Diamination of Olefins: Synthesis, Structures and Reactivity of Osmaimidazolidines

Article abstract of DOI:10.1002/chem.200305011

The diamination of certain olefins bearing electron-withdrawing substituents proceeds with well-defined bisimido and trisimido complexes of osmium. The products are obtained as osmaimidazolidines which are of unprecedented stability with regards to olefin functionalisation. Osmium complexes from related dihydroxylation or amino-hydroxylation are significantly less stable and thereby promote catalytic reactions. This difference in reaction profile has been investigated and chiral osmium heterocycles obtained from olefin difunctionalisation were characterised by X-ray analysis for the first time. Kinetic studies on the reaction profile have also been carried out. An asymmetric version of this reaction is based on chiral non-racemic auxiliaries and leads to diastereomerically enriched osmaimidazolidines with up to 90% de. This sequence represents the first asymmetric diamination of olefins. Attempts on the use of chiral ligands for direct asymmetric diamination as well as the consequences of osmaimidazolidine properties for a catalytic reaction are discussed.

Full text of DOI:10.1002/chem.200305011

FULL PAPER
Diamination of Olefins: Synthesis, Structures and Reactivity of
Osmaimidazolidines
Kilian Muniz,*[a] Atsushi Iesato,[a] and Martin Nieger[b]
ƒ
Dedicated to Professor K. H. Dˆtz on the occasion of his 60th birthday
Abstract: The diamination of certain
olefins bearing electron-withdrawing
substituents proceeds with well-defined
bisimido and trisimido complexes of
osmium. The products are obtained as
osmaimidazolidines which are of unpre-
cedented stability with regards to olefin
functionalisation. Osmium complexes
from related dihydroxylation or amino-
hydroxylation are significantly less sta-
ble and thereby promote catalytic reac-
tions. This difference in reaction profile
has been investigated and chiral osmium
heterocycles obtained from olefin di-
functionalisation were characterised by
X-ray analysis for the first time. Kinetic
studies on the reaction profile have also
been carried out. An asymmetric version
of this reaction is based on chiral non-
racemic auxiliaries and leads to diaste-
reomerically enriched osmaimidazoli-
dines with up to 90% de. This sequence
represents the first asymmetric diamina-
tion of olefins. Attempts on the use of
chiral ligands for direct asymmetric
diamination as well as the consequences
of osmaimidazolidine properties for a
catalytic reaction are discussed.
Keywords: diamination ¥ osmium ¥
stereoselective
synthesis
¥
transition-metal complexes
upon hydroxyl group activation.[2, 13] A sequence using the
double Overman rearrangement has recently been report-
ed.[14] Alternatively, synthesis of 1,2-diamines from asymmet-
ric reduction of bisimines or a-amino imines has been
described.[2, 15] Finally, a complementary biochemical ap-
proach consists of a lipase-catalysed resolution of racemic
vicinal diamines.[16]
Introduction
Vicinal diamines represent an important class of organic
compounds which are of upmost importance in various areas
of today×s chemistry including medicinal and biological
6]
chemistry,[1] asymmetric synthesis[2
and chiral oligom-
ers.[2, 3, 7] The synthesis of diastereomerically and enantiomeri-
cally pure derivatives of the 1,2-diamino group is therefore of
high importance. To achieve this purpose, a variety of
approaches have been devised.[2, 8] Apart from routine reso-
À
On the other hand, oxidative transformation of C C double
bonds represents a powerful approach towards vicinal difunc-
tionalisation. Within this area, asymmetric catalytic Sharpless
dihydroxylation (AD)[17] and aminohydroxylation (AA)[18] are
the most important achievements which have developed into
broad applicability. Nevertheless, the closely related reaction
of direct asymmetric diamination (ADA) has remained
unknown so far and even investigations into stereochemically
unselective reactions of this type have remained particularly
scarce. In 1974 Barluenga and Aznar discovered the suit-
ability of thallium(iii) salts to promote addition of anilines to
lution procedures,[2, 9] these include the asymmetric C C bond
À
formation employing reductive homo- or hetero-coupling of
imines[2, 10] and 1,2- or 1,4-addition to imines, hydrazones or
nitro olefins, respectively.[2, 8, 11] Concepts in the area of C X
À
bond formation rely on substitution reactions on carbon sp3
centres with appropriate nitrogen nucleophiles. Substrates
include aziridines[2, 12] or 1,2-diols and 1,2-amino alcohols
[19]
À
ƒ
[a] Dr. K. Muniz, A. Iesato
unfunctionalised C C double bonds. This reaction appa-
¬
Kekule-Institut f¸r Organische Chemie und Biochemie
Rheinische Friedrich-Wilhelms-Universit‰t
Gerhard-Domagk-Strasse 1
rently proceeds via aminothallation of the olefin followed by
subsequent reductive dethallation by
a second amine
[Scheme 1, Eq. (1)]. A related reaction sequence by B‰ckvall
employed palladium(ii) and lead(iv) to promote addition of
aliphatic amines to simple olefins [Eq. (2)].[20] Sharpless× use
of preformed bis- and trisimidoosmium complexes allowed
reaction with fumaric esters and both aromatic (styrene) and
aliphatic olefins [Eq. (3a)].[21] Later, Schrock described the
application of a related compound bearing a sterically
hindered aromatic imido substituent that reacted with ethyl-
53121 Bonn (Germany)
Fax : (‡49)0228-73-5813
E-mail: kilian.muniz@uni-bonn.de
[b] Dr. M. Nieger
X-ray Structure analysis:
Institut f¸r Anorganische Chemie
Gerhard-Domagk-Strasse 1
53121 Bonn (Germany)
E-mail: nieger@joyx.joensuu.fi
Chem. Eur. J. 2003, 9, 5581 5596
DOI: 10.1002/chem.200305011
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ƒ
K. Muniz et al.
FULL PAPER
ene, norbornene and cyclopentene to give diamine derivatives
as the sole products.[22] Moreover, the shown compound
derived from reaction with ethylene has been the only one of
these derivatives that had been characterised by X-ray
analysis [Eq. (3b)].[22c] Finally, Barluenga devised the use of
mercury(ii) salts for a diamination reaction similar in nature to
the thallium mediated one [Eq. (4)].[23]
of the three imido compounds 1, 2 and 3. This crude mixture
can be separated on silica gel chromatography to yield the
desired complexes 2 and 3 in yields of around 40and 15%,
respectively. The monoimido complex 1, which is isolated in
40% yield, can be re-submitted to reaction with N-trimethyl-
silyl tert-butyl amine to yield a further amount of 2 and 3 (28
and 53% yield, respectively, on a 5 mmol scale).
Within this approach, the different imido complexes can be
conveniently distinguished from their respective NMR spec-
tra. As had been described for 1 and 2 by Nugent and
Haymore,[31] the relative difference in shift DdC as observed
from the respective 13C NMR can be correlated to the relative
electron density at OsVIII. Thus, it can be related directly to the
number of amino moieties present in the complex, a trend that
is apparently maintained in going from 2 to 3. The respective
shifts for the signals of the methyl and the quaternary carbon
atoms and the corresponding shift differences are given in
Scheme 2.
Scheme 1. Metal-mediated diamination of olefins.
Scheme 2. Synthesis of osmium imido complexes.
Ever since, no further investigation into the area of metal-
mediated diamination of olefins has been undertaken and a
related catalytic diamination of olefins has yet to be devel-
oped. So far, there have been disparate reports on reactions
from which diamines have been isolated either as by-products
in aziridinations[24] or as the result of solvent incorporation in
reactions with Ritter-type termination.[25, 26]
We have recently reported on a first stoichiometric
asymmetric diamination of fumaric and acrylic esters[27] as
well as on the synthesis of an osmaimidazolidine as ligand for
asymmetric catalysis[28]and here wish to present a full account
of this work as well as a detailed analysis on the reaction
profile of this diamination and of the structural properties of
osmaimidazolidines.
Reactions of bisimido osmium(viii) complex 2: As expected,
the reaction of 2 with simple olefins is rather slow resulting in
relatively low chemical yields. Certainly, the use of electron-
poor olefins as substrates is of greater interest since the
respective reaction rates are higher; there had been a previous
report that the products from reactions with fumarates are
characterised by a more enhanced stability.[21] Thus, it was
decided to investigate the scope of the diamination of olefins
bearing electron-withdrawing substituents.
Acrylic esters: The reaction between 2 and methyl cinnamate
4 was chosen for elucidation of optimum reaction conditions.
The reaction was relatively unaffected by changes in the
conditions. It proceeds with over 75% chemical yield in
various solvents ranging from dichloromethane or THF and
dioxane to benzene and toluene. Concentrations between 0.1
and 2 molar in olefin have no influence on the yield. In
solvents such as benzene and THF the reaction even proceeds
under ambient atmosphere. If not stated otherwise, all
reactions described in this article were carried out in THF
and under Ar. Moreover, it was found that for a ratio of 4:2 in
the range of 1.0to 2.0, the reaction outcome is independent of
the amounts of olefin present. Thus, 1.2 equivalents of olefin
were generally used (given yields are based on the amount
of 2).
Results and Discussion
Synthesis of OsVIII-imido complexes: The conversion of
osmium tetroxide into bis- and trisimido species had first
been investigated by Sharpless who favoured a two-step
procedure involving the synthesis of the mono-imido complex
1 from aqueous tert-butyl amine followed by subsequent
further imination with the aid of phosphane iminates.[21] Later
reports by Nugent[29] and Wilkinson[30] on the direct synthesis
of 2 and 3 relied on the use of N-trimethylsilyl tert-butyl
amine.
Under these conditions, various olefins were converted into
osmaimidazolidines with excellent yields (Scheme 3, Table 1).
Within this series of reactions the use of methyl, benzyl and
tert-butyl cinnamate gave the corresponding diamination
In our hands, it turned out most convenient to directly treat
an n-hexane solution of osmium tetroxide with a 20- to 25-fold
excess of N-trimethylsilyl tert-butyl amine to obtain a mixture
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Diamination of Olefins
5581 5596
Scheme 3. Diamination of acrylic esters with bisimido complex 2.
Table 1. Diamination of acrylic esters.
Substrate
R
R'
Yield [%][a]
Product
1
2
3
4
5
6
7
8
4
5
6
7
8
9
10
11
C6H5
C6H5
C6H5
CH3
CH3
H
CO2CH3
3-pyridinyl
CH3
94
96
89
91
92
98
90
78
12
13
14
15
16
17
18
19
C(CH3)3
CH2C6H5
CH3
C2H5
CH3
CH3
CH3
[a] Isolated yield after column chromatography.
products 12 14 with the three orthogonally protected esters.
In similar reactions, crotonates 7, 8 and acrylate 9 gave clean
reactions to furnish the respective diamination products in
high yields. Another of the results from Scheme 3 is of
particular interest. Diamination of 3-pyridyl methyl acrylate
11 gave the corresponding osmaimidazolidine 19 in 78%
isolated yield after column chromatography. In related
osmium-mediated or catalysed dihydroxylation or amino-
hydroxylation reactions,[32] compounds displaying a free
pyridine nitrogen constitute a problematic class of substrates
either since they undergo coordination to the osmium
reagent[33] or because they suffer from oxidation of the
pyridine nitrogen under catalytic conditions. However, in the
present case, no competitive products could be isolated
indicating that the pyridinyl moiety does not exercise any
deleterious effect.
Figure 1. Solid-state structure of osmaimidazolidine 12. Selected bond
À
À
À
lengths [ä] and angles [8]: Os1 O1 1.731(2), Os1 O2 1.722(2), Os1 N1
À
1.881(2), Os1 N4 1.881(2), N1-Os1-N4 82.40(10), O1-Os1-N1 112.50 (10),
O2-Os1-N1 111.85(10), O2-Os1-N4 113.13(9).
In all these examples and for the related examples discussed
below, the diamination reaction turned out to be both highly
stereospecific and highly chemoselective. All spectroscopic
investigations on the crude reaction mixtures displayed only
trans-configured osmaimidazolidine products 12 19 proving
that the original geometry of the olefin was preserved.
Identically, the formation of diol or amino alcohol products
originating from the competitive addition of oxo ligands was
never observed indicating that the bisimido complex 2
exclusively transfers its two amino groups to the olefinic
substrate. Given the high stability of the resulting osmaimi-
dazolidines it was possible to obtain X-ray quality crystals for
several of the products. Two examples, the solid-state
structures of complexes 12 and 13, are depicted in Figures 1
and 2 (data on these structures are given in Table 5) and
represent the first structural elucidations of chiral osmaimi-
dazolidines.
For the diamination of electron-deficient olefins there is no
major electronic influence on reaction rate as could be
determined from a competition experiment. When a C6D6
solution containing equal amounts of dimethyl fumarate (10)
and methyl cinnamate (4) was added to reaction with one
equivalent of 2, NMR analysis showed that both products 12
and 18 were formed in about equal amounts at every stage of
the reaction between 17 and 92% conversion. This result
Figure 2. Solid-state structure of osmaimidazolidine 13. Selected bond
À
À
À
lengths [ä] and angles [8]: Os1 O1 1.721(3), Os1 O2 1.731(3), Os1 N1
À
1.881(4), Os1 N4 1.884(4), N1-Os1-N4 82.27(15), O1-Os1-N1 111.64(16),
O2-Os1-N1 111.86(16), O2-Os1-N4 110.90(16).
proves that evidently one carbonyl group is sufficient in order
to achieve maximum reaction rate for the diamination.
Dimethyl maleinic ester 20 underwent diamination in the
presence of 2 (Scheme 4). However, this reaction proceeded
at very low rate and appeared to be solvent dependent since
product formation was only detected for a reaction in THF.
Moreover, a mixture of the expected syn-configured com-
pound 21 and its corresponding trans-isomer 18 was isolated.
The latter one was identified from its characteristic set of
signals which were identical to the ones from the authentical
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which are generally of notorious
sensitivity,[35] complex 33 does not
suffer any stereochemical changes
upon exposure to base or weak
acids and the trans-configuration is
maintained at all time. This again
confirms that the trans-arrange-
ment represents the thermodynam-
ically preferred configuration for
Scheme 4. Diamination of maleic ester 20.
osmaimidazolidines.
In an otherwise identical diami-
sample derived from diamination of dimethyl fumarate 10
with 2. Importantly, the original ratio of 1.3:1 in favour of 21
(determined by proton NMR from the crude reaction
mixture) was found to have been reversed to 1:1.7 after
column chromatography. Apparently, under the reaction
conditions, equilibration of the primarily formed product 21
takes place, which is enhanced further during purification on
silica gel. Isolation of a pure sample of compound 21 was
nation reaction, acrylonitrile (34) was transformed into the
corresponding 4-cyano-substituted osmaimidazolidine 35
which was isolated in 76% yield.
Again, all products described were of high stability and two
of them, complexes 28 (Figure 3) and 32 (Figure 4), were
characterised in the solid state. Their overall stereochemical
features coincide well with the ones of 12 and 13 depicted
1
therefore not possible and its H NMR characterisation was
carried out by subtractions of the signals of the known
compound 18. Finally, treatment of the 1:1.7 mixture of 21:18
with triethylammonium chloride resulted in complete equili-
bration and complex 18 was isolated as sole compound. This
indicates that conversion of 21 to the thermodynamically
stable trans-configured complex 18 is indeed the decisive
process.[34]
Further carbonyl derivatives: After the synthesis of osmaimi-
dazolidines by diamination of acrylic esters had been estab-
lished, we turned our attention towards the related electron-
deficient olefins. In particular, the functional groups of
amides, ketones and aldehydes were studied. In all these
cases, the respective osmaimidazolidines were obtained as
sole products and in high chemical yields (Scheme 5, Table 2).
This is a noteworthy feature of this chemistry since related
Figure 3. Solid-state structure of osmaimidazolidine 28. Selected bond
À
À
À
lengths [ä] and angles [8]: Os1 O1 1.729(3), Os1 O2 1.725(3), Os1 N1
À
1.881(3), Os1 N4 1.878(3), N4-Os1-N1 82.49(14), O1-Os1-N1 108.56(14),
Scheme 5. Diamination of electron-deficient olefins.
Table 2. Diamination of electron-deficient olefins.
O2-Os1-N1 113.03(14), O2-Os1-N4 110.95(15).
above. Their most important characteristics are the pseudo-
tetrahedral coordination at the central Os atom and the
Substrate
R
R'
Yield [%][a]
Product
À
À
relatively small difference in Os O double bond and Os N
bond. For the former, values in the usual range of 1.7 ä were
determined while the latter showed bond lengths of about
1
2
3
4
5
6
22
23
24
25
26
27
C6H5
CH3
H
C6H5
C6H5
C6H5
NHC(CH3)3
NHC(CH3)3
NHC(CH3)3
NCH3(OCH3)
C6H5
89
86
89
84
91
92
28
29
30
31
32
33
À
1.88 ä. This indicates significant p-character for the Os N
bonds and points to an increased stability of the osmium
diamino chelate structure.
H
[a] Isolated yield after column chromatography.
From a structural point of view, the stability of all these
products is amazing. First, their monomeric character is
unprecedented. As it had already been observed by Crie-
gee,[33] that related glycolate complexes of OsVI resulting from
dihydroxylation reactions are lacking electronic stabilisation
and thus convert into more stable bisglycolate derivatives.[36]
Monoglycolates can only be stabilised by additional coordi-
osmium-mediated or catalysed reactions do not tolerate many
of these functional groups.[17, 18] As an important result,
À
bisimido osmium reagent 2 selectively oxidises the C C
double bond in 27 leaving the aldehyde function intact. In
contrast to the configurational stability of a-amino aldehydes
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Diamination of Olefins
5581 5596
Reactions of trisimido osmium(viii) complex 3 with olefins:
Within the reaction of the related trisimido complex 3
investigation has been limited to fumaric esters. Diamination
of dimethyl fumarate (10) had already been described by
Sharpless in 1977.[21] Under the present reaction conditions,
this substrate and the related diethyl ester gave excellent
product formation (Scheme 6). However, unlike the case with
the bisimido reagent 2, complex 3 did not give any detectable
product from reaction with maleic ester 20. Again, the tert-
butylimido-oxoosma(vi)imidazolidine products 36 and 38 are
stable, deep red solids that cannot be re-oxidised to OsVIII with
common homogeneous oxidants such as hydrogen peroxide,
chloramine-T or N-methyl morpholine N-oxide.
Figure 4. Solid-state structure of osmaimidazolidine 32 (hydrogen atoms
À
are omitted). Selected bond lengths [ä] and angles [8]: Os1 O1 1.716(3),
À
À
À
Os1 O2 1.715(4), Os1 N1 1.880(4), Os1 N4 1.886(4), N1-Os1-N4
81.45(15), O1-Os1-N1 111.79(17), O2-Os1-N1 111.80(18), O2-Os1-N4
114.23(15).
Scheme 6. Diamination of fumarates with trisimido complex 3.
In contrast to the data for related dioxo complex 18, careful
examination of the NMR spectra revealed a pronounced non-
symmetry for the signals both of the hydrogen atoms and the
carbon atoms of the heterocyclic part of the osmaimidazoli-
dine. This is not surprising since the arrangement at Os locates
the oxo and the imido ligand on different sides of the
osmaimidazolidine and thus enforces non-equivalency of the
incorporated atoms and functional groups.
In order to get a further insight into the relative behaviour
of 1 3 towards electron-deficient olefins, the oxidation of
dimethyl fumarate (10) was investigated. First, the thus far
unknown reaction of 1 with this olefin gave a complicated
product mixture.[45] Since glycolate osmate esters and their
monoaza derivatives are generally known to display only
limited stability,[17, 18, 33] the reaction was worked up with an
aqueous Na2SO3 solution. From this, dimethyl tartrate 39 and
its monoaza analogue 40 were identified and were present in a
ratio of 1:6 which shows that 1 does not oxidise 10 in a
chemoselective fashion (Scheme 7). It is widely accepted that
the chemoselectivity of monoimido osmium(viii) compounds
can be correlated to the electron density at Os. For example,
for 1 the aminoalcohol/diol ratios can be greatly increased
upon coordination of tertiary amine ligands to the osmium
reagent.[18, 46] This effect is maintained for moderate electron
acceptor imido-substituents such as tosylate, carbamates and
amides, but is reversed for stronger electron acceptors, either
nation of s-donors such as pyridines,[37] Cinchona alkaloids,[38]
and diamines[4a, 39] or by dimerisation.[40] These results also
apply for the corresponding azaglycolates as products from
aminohydroxylation of olefins.[41]
The observed stability of monomeric osmaimidazolidines is
À
the direct consequence of the electron-rich Os N bonds and
their inherent double-bond character which accounts for a
formal 16 to 18 electron Os centre. Moreover, some of these
osmaimidazolidines were of particular interest for comparison
with the related glycolate and azaglycolate osmium com-
plexes. For example, the amides 28 31 were stable even
under prolonged exposure to aqueous oxidative solutions.
Thus, when a 2m solution of 28 in tetrahydrofuran was treated
with amine N-oxides or an aqueous solution of chloramine-T
and heated for 24 h, the osmaimidazolidine was recovered
unchanged and in nearly quantitative yield. Under otherwise
identical conditions, related azaglycolate osmium complexes
bearing residual amido moieties are known to undergo
spontaneous reoxidation, olefin functionalisation and subse-
quent hydrolysis.[42] This chemistry has been the basis for
recent development of secondary cycle osmium catalysis.[43]
Apparently, the inherent stability of osmaimidazolidines of
28 31 in general owes to the electronic saturation of the OsVI
centre that prevents reoxidation to OsVIII. Any type of
diamine hydrolysis would only result after osmium reoxida-
tion, however, it is the strength of the diamine osmium
À
chelate and the additional Os N double bond character that
prevents this prerequisite step. Moreover, various other
À
attempts to cleave the osmium nitrogen bonds remained
unsuccessful. These included use of reducing agents such as
sodium sulfite or sodium thiosulfate. Removal of the osmium
centre was found to be possible only by interaction with strong
hydride reducing agents such as lithium aluminium hydride or
sodium borohydride.[27, 44]
Scheme 7. Competitive oxidative functionalisation of 10 with 1.
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due to loss of reactivity of the imido-ligand transfer itself or to
its direct hydrolysis. In these cases, diol by-product is formed
in significant amounts and can dominate the reaction as a
whole. For example, in the presence of haloamine salts
derived from trifluoroacetamide dihydroxylation becomes the
exclusive pathway.[47] In accord with this, the increase in
electron density at osmium in going from 1 to 3 as already
deduced from the relative difference in D13C NMR shifts
results in a dramatic increase in chemoselectivity and contra-
rily to 1, compounds 2 and 3 give diamination products
exclusively.[21, 27]
reagents, imido osmium(viii) reagents 1 3 appear to be
unique since attempts to react acceptor-substituted olefins
such as 4 and 10 with methyl tris(tert-butylimido)rhenium(vii)
and related compounds[48, 49] gave no detectable diamination
at all.[47]
Diastereoselective transformations: Given the successful
diamination of acrylic esters and related compounds, chiral
enantiopure derivatives should serve as suitable substrates for
diastereoselective diamination reactions of this type.[50] Such
an appproach which would be an example of chiral auxiliary
directed asymmetric synthesis between a non-racemic olefin
and an achiral diaminating reagent was investigated for the
case of enantiopure alcohols. It had already been used for the
parent dihydroxylation to convert chiral olefins to diaster-
eomerically enriched or pure diol derivatives.[51, 52] Interest-
ingly, there is only one example regarding a stereoselective
olefin functionalization that employs the monoimido com-
pound 2 or related in situ generated imido complexes and
naturally occurring terpenes as chiral non-racemic starting
material.[53] A chiral cinnamate had been investigated already
in 1989 within a stoichiometric aminohydroxylation of 13-
cinnamoyl baccatin III. However, the reaction was unselec-
tive and yielded all four diastereoisomers.[54]
The overall reaction profile was investigated in a competi-
tion experiment in THF with 3 mmol dimethyl fumarate (10)
and 1 mmol each of the respective oxidants 1 3. The reaction
proceeding was monitored with samples being taken every
1
hour, worked-up and analysed by H NMR. Given the low
conversion of 1, tartrate amounts were below the detection
level. The relative amino alcohol formation originating from 1
turned out to be relatively slow (27% conversion of 1 after
3 h). Osmaimidazolidine formation with 2 and 3 occurred at
higher, albeit different rates (Figure 5).
For the present purpose, incorporation of a chiral non-
racemic auxiliary into the ester functionality could devise a
route towards stereoselective diamination via differentiation
À
of the diastereotopic sides of the C C double bond. For
example, (À)-menthol, 1-phenyl ethanol, (‡)-fenchol and the
Oppolzer sultam all gave the osmaimidazolidine complexes
42 and 43 with moderate diastereomeric ratios ranging from
1:1 to 2.6: 1 (Scheme 8).
Figure 5. Competition experiments for oxidation of dimethyl fumarate
(10) with osmium reagents 1 3. Formation of 39 was below detection level.
The relative rates were investigated within a second
experiment. Here, diamination in the presence of an excess
amount of 10 (10mmol) was carried out with 1 mmol each of 2
and 3. Interestingly, diamination with 3 appears to proceed
with higher rate than the related reaction with 2, despite the
potentially disadvantageous bulk from the additional tert-
butyl imido substituent of the former reagent. Therefore, most
probably, the relative increase of reactivity from 1 to 3 has its
basis in the increased electron density at the respective Os
centres. Currently, this conclusion remains limited to the
present case of electron-deficient olefins since the behaviour
of the respective ratios regarding aminohydroxylation and
diamination, and competitive diamination appear to be
substrate-depending.[47] Within this context, one should also
note the general importance of substrate geometry: while
OsO4 in AD reactions shows a high preference for electron
rich or neutral (Z)-olefins, monoimido osmium derivatives
for AA reaction tend to prefer electron-demanding (E)-
olefins. This is further pronounced for the present stoichio-
metric diamination reaction which strongly favours electron-
deficient (E)-olefins.[21, 27] Consequently, dimethyl maleic
ester reacts extremely slowly with 2 and is unreactive with 3.
Noteworthy, for the purpose of olefin diamination with imido
Scheme 8. Auxiliary screening for asymmetric osmaimidazolidine forma-
tion.
Table 3. Diastereomeric ratios for diamination with selected chiral auxil-
iaries. The absolute configuration in products 42a c,e and 43a c,e are
undetermined.
Substrate
X*H
Ratio 42:43[a]
1
2
3
4
5
41a
41b
41c
41d
41e
1-phenyl ethanol
campher sultame
(À)-menthol
1:1
2.6:1
1.5:1
3.2:1
1.4:1
(À)-8-phenyl menthol
fenchol
1
[a] Determined from H NMR spectra of the crude reaction mixture.
From this auxiliary screening, 8-phenyl menthol was found
to give the best results as summarized in Table 3. While this
reagent induced only a moderate 78:22 diastereomeric ratio
for 42d:43d at 308C, this value could be significantly
improved to up to 94:6 when the reaction was carried out at
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Diamination of Olefins
5581 5596
Table 4. Diastereomeric ratios for diamination with (À)-8-phenyl menthol
as chiral auxiliary.
Substrate
R
Yield [%][a]
Product ratio[b]
1
41a
41a
44
47
47
C6H5
C6H5
CH3
H
68
56
81
96
88
78:22 (42d/43d)
94:6 (42d/43d)
72:28 (45/46)
88:12 (48/49)
95:5 (48/49)
2[c]
3
4
5[c]
H
[a] Diastereomeric mixture after column chromatography. [b] Determined
by analytical HPLC. [c] The reaction was run at À158C.
Scheme 9. Asymmetric diamination with (À)-8-phenyl menthol as chiral
auxiliary [R*OH ˆ (À)-8-phenyl menthol].
Figure 6. Solid-state structure of major diastereoisomer 42d.[27] Selected
À
À
bond lengths [ä] and angles [8]: Os1 O1 1.726(4), Os1 O2 1.727(3),
À
À
Os1 N1 1.884(4), Os1 N4 1.896(4), N1-Os1-N4 81.14(18), O1-Os1-N1
110.96(18), O2-Os1-N1 113.64(18), O2-Os1-N4 110.03(19).
À158C (Table 4, Scheme 9). However, this increase in dr was
accomplished by a significantly lower reaction rate and a
period of 36 h was required to reach a combined yield of 56%.
As observed for the related achiral substrates discussed
above, no solvent dependence was observed and diaminations
in dichloromethane and benzene gave nearly identical ratios
for 42d:43d. Attempted column chromatographic separation
of the two diastereomers proved difficult and semipreparative
HPLC was preferential for their complete separation.
At room temperature, the crotyl derivative 44 gave a
comparable diastereomeric ratio of 72:28 for 45:46. Interest-
ingly, the mono-substituted acrylic ester 47 yielded an
improved ratio of 88:12 for 48:49 and proceeded at higher
rate. Again, lowering the temperature to À158C had a
beneficial effect on diastereoselectivity and the two diamina-
tion products 48/49 were obtained with 95:5 dr. The X-ray
structure of the major diastereoisomer 42d has been report-
ed.[27] An ORTEP plot is depicted in Figure 6.
LAH reduction of the diastereomerically pure complexes 42d
and 43d, repectively.[27] In order to obtain enantiomerically
pure metal-free diamino amides from NaBH4 reduction, it
turned out necessary to convert the osmaimidazolidine ester
groups into their corresponding amides. This transformation
was achieved by using a substoichiometric amount of zinc(ii)
chloride (25 mol%) and the amine as solvent (Scheme 10).
Scheme 10. Functional group transformation of osmaimidazolidines.
The observed configuration for this major isomer is in
agreement with a stereochemical transition state in which the
À
diastereotopic Si face of the reactive C C double bond is
After 36 hours at 758C, the desired amides 28 and 29 were
isolated in good yields (67 and 72%, respectively, together
with unreacted starting material). Analysis by analytical
HPLC confirmed that the new compounds had not undergone
racemisation.[57] However, when related N-alkylated a-amino
acids were added under the same conditions, significantly
lower reaction rates for amide formation were observed.[47]
selectively shielded by the adjacent phenyl moiety of the
chiral terpene auxiliary. Thus, diamination occurs preferen-
tially from the more accessible Re face of the olefin furnishing
the observed 4R,5S-configuration for the major diastereomer,
a reaction outcome that is reminiscent of an AD reaction on
methylacrylates.[51b] Such a stereochemical model A of a p-
stacking interaction had first
À
Certainly, in case of epimerization at the C H acidic centre in
been suggested by several
groups for diastereoselective
reactions of 8-phenyl menthyl
acrylates,[55] among which the
most pronounced example is on
Fischer carbene complexes as
chiral Michael acceptors.[56]
Chiral, non-racemic diamino
alcohols could be obtained in
both enantiomeric forms from
a-position to the carbonyl moiety the resulting syn-configured
osmaimidazolidine re-isomerises to the thermodynamically
stable trans-isomer as it had already been observed in case of
the complexes 18 and 21 (see above). However, since the
second stereogenic centre is not prone to epimerisation, its
absolute configuration determines the regeneration of the
overall trans-arrangement and thus the original absolute
configuration as originating from the starting material is
preserved. In accord with this observation, a related trans-
formation on the mono-substituted, diastereomerically pure
Chem. Eur. J. 2003, 9, 5581 5596
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FULL PAPER
osmaimidazolidine 17 led to a sample 30 which displayed only
a low enantiomeric excess of 67%. Thus, enantiomerically
pure samples of 28 and 29 are available that can be converted
to enantiopure diamino carbamides as described previous-
ly.[27]
In view of the excellent reactivity of the imido complexes 2
and 3 towards alkyl fumarates their reaction with a chiral non-
racemic analogue, the commercially available bis[(À)menth-
yl] fumarate (50), was investigated as well (Scheme 11).
approach that is opposite to the one in the related case
employing the 8-phenyl-menthyl auxiliary. This latter auxil-
iary dominates the stereoselective diamination via an active
p-stacking conformation that apparently overrides the given
preference in stereodiscrimination with the (À)-menthyl
moiety. The oxidative conversion of chiral fumarate 50 has
been previously described to occur with oxidants such as
osmiumtetroxide[58] and potassium permanganate[59, 60] yield-
ing mixtures of diastereomers with an analogous preference
for the (R,R)-diastereomer,[59]
albeit with lower dr. Regarding
the structure of 53 itself, it is
important to note that the re-
maining imido ligand coordi-
nates in a bent fashion of an
1578 angle. This indicates that
the ring nitrogen atoms contrib-
ute most of the electronic sta-
bilisation to the Os centre and
the imido ligand is involved
Scheme 11. Diastereoselective diamination of bis[(À)-menthyl] fumarate (50) [R*OH ˆ (À)-menthol].
only to a much lower extend.
In contrast, Schrock×s arylimido
Thus, its reaction with 2 led to diastereomers 51 and 52 in a
ratio of 81:19. This ratio could be significantly increased when
complex 2 was changed for the trisimido derivative 3 and
products 53 and 54 were isolated in >95: < 5 dr.[27] The
absolute configuration of the products was unambigously
determined from an X-ray analysis of the major diastereomer
53 (Figure 7) as R,R. Understanding that there should be no
osmaimidazolidine structure[22b] displays a nearly linear imido
À
À
ligand with an N Os C angle of 1788 indicative of a reversed
electron donation via the imido lone pair.
A chiral catalyst obtained from 53 was described recently
and represents the first successful application of an osmaimi-
dazolidine based chiral ligand in asymmetric catalysis.[28] It
also showed that removal of the tert-butyl entities might not
be necessary in order to transform the diamination product
into useful compounds for further asymmetric synthesis.
Enantioselective transformations: The successful use of
Cinchona alkaloid derivatives of dihydroquinine and dihy-
droquinidine in related reactions of dihydroxylation[17] and
aminohydroxylation[18] is well-documented and prompted use
of these compounds as ligands in the present diamination
reaction. The resulting osmacycles were submitted directly to
HPLC analysis since the required manipulation for release of
the diamino moiety was considered inappropriate. For 2,2-
diooxo osmaimidazolidines 11 and 59, and for tert-butylimido
osmaimidazolidine 36 enantiomers could be separated on
analytical chiral HPLC. However, regardless whether DHQD
or DHQ derivatives were used as chiral ligands for diamina-
tion with 2 or 3, no asymmetric induction could be obtained
and all products isolated from these runs in the presence of
potential ligands 55 58 were essentially racemic
(Scheme 12).
1
Careful H NMR titration studies for different ratios of 2
Figure 7. Solid-state structure of major diastereoisomer 53 (except for the
stereogenic centres at C4 and C5, hydrogen atoms are omitted). Selected
and the standard first-generation PCB ligand of DHQD (57)
did not suggest any complexation at all. Apparently, even in
the presence of a 20-fold excess of DHQD-CLB 57 there was
no change in the NMR shifts of the respective set of signals for
the two compounds. This is a pronounced difference to the
related situation for both osmiumtetroxide and the mono-
imido complex 1 which form Cinchona alkaloid complexes
that can be detected spectroscopically. For these two Os
compounds, an equilibrium between the free complex and the
ligated derivative has been established.[46, 61] Such a behaviour
À
À
bond lengths [ä] and angles [8]: Os2 O1 1.707(6), Os2 N2 1.727(7),
À
À
Os2 N3 1.887(8), N1 Os2 1.893(7), N2-Os2-N3 112.5(3), O1-Os2-N1
110.6(3), O1-Os2-N2 115.5(3), N3-Os2-N1 81.9 (3), C36-N2-Os2 157.4(6).
severe difference in the course of diamination reactions with 2
and 3, respectively, an identical absolute configuration is
assumed for the dioxo derivative 51. It is important to note
that the (R,R)-configuration results from Si face addition, an
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Diamination of Olefins
5581 5596
surface for all reactive intermediates.[63] The drastic increase
in stability of osmaimidazolidines as primary products of the
diamination prevents such a scenario. Given the current
stability of N,N'-dialkyl osmaimidazolidines the development
of catalytic reactions proceeding at efficient rates remains
challenging. Thus, the search for bistosylimido derivatives of
osmium(viii) and for defined osmaimidazolidine complexes of
similar lability as their glycolate and azaglycolate osmate
esters, respectively, constitutes the present focus of ongoing
research.
Conclusion
A detailed investigation on the diamination of electron-poor
olefins by means of preformed bis- and trisimido osmium
reagents has been described. The products were obtained as
osmaimidazolidines with a pronounced stability. The latter
fact has been correlated to an enhanced electronic saturation
at the osmium centre due to donation from the basic free lone
pair at the ring nitrogen atoms. This electronic effect renders
the chemistry of osmaimazolidines different from the one of
its glycolate and azaglycolate osmate ester counterparts. The
most significant consequences are the stability of the resulting
OsVI centre towards reoxidation and the inherent stability
towards hydrolytical cleavage of the monomeric Os diamine
entity. At present, the development of catalytic versions on
the basis of the described chemistry appears problematic. A
first asymmetric diamination of olefins has been developed by
using chiral non-racemic auxiliaries that led to the isolation of
diastereomerically enriched osmaimidazolidines that can be
transformed by defined chemical transformations.
Scheme 12. Attempts towards an asymmetric diamination employing
Cinchona alkaloid ligands.
which is indispensable for ligand-accelerated catalysis[62] can
prove rather problematic in asymmetric stoichiometric trans-
formations. In such case, tight binding between ligand and
metal centre is preferable. The inability of bis- and trisimido-
complexes 2 and 3, respectively, to undergo complexation to
Cinchona alkaloids results from the tert-butylimido ligands at
osmium. Since these entities contain a basic lone pair at each
nitrogen of the imido ligand, donation of electron density to
the formally 16e-osmium centre is enhanced and results in a
significantly diminished Lewis acidity at the metal centre, if
any. As a consequence, no s-coordination of external ligands
is feasible. This result also explains the apparent ease of
diamination of pyridyl acrylate 11 since a potentially com-
peting coordination of the pyridino group to the OsVIII reagent
cannot take place.
In view of the difficulties that have been encountered in the
stoichiometric diamination reaction, a potential catalytic
diamination will require the involvement of more labile
osmaimidazolidine complexes. This might be achieved from
use of a bistosylimido compound or related complexes,
however, removal of the product diamine from the osmium
centre will then require anhydrous conditions and use of an
amino or amido compound as a discrete precursor to an imido
moiety at osmium. The elaboration of such catalytic cycles
depends crucially on an equilibrated potential energy level
Experimental Section
General: Osmium(viii) oxide was purchased from Strem. tert-Butylamine,
N-trimethylsilyl tert-butylamine, methyl cinnamate, benzyl cinnamate,
metyl acrylate, chalcone, bis[(À)-menthyl] fumarate, (DHQD)2PHAL
and (DHQ)2PHAL were purchased from Fluka. Cinnamoyl chloride,
3-pyridine acrylic acid, cinnamic aldehyde, methyl crotonate, ethyl
crotonate, dimethyl fumarate, diethyl fumarate, dimethyl maleic ester,
zinc chloride, (À)-8-phenyl menthyl and phenyl magnesium chloride (2.0m
solution in THF) were purchased from Aldrich. The following compounds
were synthesised following literature procedures: tert-butyl cinnamate,[64]
N-tert-butyl cinnamide,[65] N-tert-butyl crotonamide,[66] N-tert-butyl acryl-
amide,[67] N-methoxy, N-methyl cinnamide,[68] 1-phenylethyl cinnamate,[69]
DHQ-PCB[17a, 61] and DHQD-PCB.[17a, 61]
THF, n-hexane and toluene were distilled from sodium/benzophenone
under argon and saturated with argon. Dichloromethane and triethylamine
were distilled from CaH2 under argon. All other solvents were reagent
grade and used as received. If not stated otherwise, ™standard work-up∫
refers to evaporation of the solvent under reduced pressure. Column
chromatography was performed with silica gel (Merck, type 60, 0.063
0.2 mm and Machery Nagel, type 60,
0.015 0.025 mm). The numbering on
the osmaimidazolidines was carried
out as depicted at the right in agree-
ment with a prior publication.[27]
Optical rotations were measured on a
Perkin Elmer 341 polarimeter. Con-
centrations are given in g per 100 mL as dichloromethane solutions. NMR
spectra were recorded on a Bruker DPX 300 MHz and Bruker DRX
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FULL PAPER
‡
500 MHz spectrometer. All chemical shifts in NMR experiments are
reported as ppm downfield from TMS. The following calibrations were
used: CDCl3 d ˆ 7.26 and 77.00 ppm, C6D6 d ˆ 7.16 and 128.00 ppm. IR
spectra were recorded on a Nicolet Magna 550FT-IR spectrometer. MS
and HRMS experiments, and elemental analysis were performed on a
Kratos MS 50and a Elementar Analysensystem Vario EL, respectively,
m/z (%): 528 (22) [M] , 513 (28), 469 (100), 413 (90), 357 (41); HRMS:
calcd for C18H28N2O4188Os: 524.1608, found: 524.1606.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(tert-butyloxycarbonyl)-2-
osma(vi)imidazolidine (13): Obtained as described above from reaction
between tert-butyl cinnamate (1.14 g, 5.59 mmol) and complex 2 (1.7 g,
4.66 mmol) in THF (10mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
diethyl ether 10:1) gave the title compound as a red solid (2.55 g,
4.47 mmol, 96%). 1H NMR (300 MHz, C6D6): d ˆ 1.12 (s, 9H), 1.19 (s,
¬
within the service centres at the Kekule-Department, Bonn. HPLC
determinations were carried out on a Knauer Wellchrome (injection valve
A0258, pumpK À 100, solvent organizerK-1500, UV-detector K-2600).
Data for crystal structure analysis were measured on a Nonius Kappa CCD
diffractometer.
1
9H), 1.39 (s, 9H), 4.15 (s, 1H), 4.98 (s, 1H), 7.12 7.24 (m, 5H); H NMR
(300 MHz, CD2Cl2): d ˆ 1.14 (s, 9H), 1.21 (s, 9H), 1.41 (s, 9H), 4.18 (s, 1H),
5.00 (s, 1H), 7.16 7.22 (m, 5H); 13C NMR (75 MHz, C6D6): d ˆ 27.96, 29.94,
30.84, 66.79, 67.49, 81.99, 82.61, 86.26, 126.77, 127.68, 128.85, 146.43, 172.00;
13C NMR (75 MHz, CD2Cl2): d ˆ 26.95, 28.95, 29.77, 66.34, 67.06, 81.38,
81.48, 84.75, 125.62, 126.95, 127.77, 144.91, 170.82; IR (KBr): nÄ ˆ 2978, 1714,
Synthesis of imido osmium(viii) complexes from osmium tetroxide: N-
Trimethylsilyl-tert-butylamine (9.0mL, 47 mmol) was added via syringe to
a solution of (1.00 g, 3.9 mmol) of OsO4 in freshly distilled n-hexane. The
mixture was stirred for 14 h at 308C after which all volatile materials were
removed under reduced pressure and the remaining dark brown residue
was purified by column chromatography (silica gel, CH2Cl2) to yield, after a
small first fraction of starting material, a broad yellow band that contained
the monoimido complex. Changing the eluent to CH2Cl2/EtOAc (80:20)
gave an orange band containing the bisimido complex 2. The trisimido
complex 3 was eluted as a dark red band by changing to EtOAc. Removal
of the solvents under reduced pressure left the respective imido complexes
that were stored under Ar at 28C.
1365, 1298, 1184, 1155, 904, 891 cmÀ1; MS (EI): m/z (%): 570(8) [ M] , 469
‡
(100), 413 (79), 357 (38); HRMS: calcd for C21H34N2O4188Os: 566.2077,
found: 566.2085.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(benzyloxycarbonyl)-2-os-
ma(vi)imidazolidine (14): Obtained as described above from reaction
between benzyl cinnamate (286 mg, 1.2 mmol) and complex 2 (364 mg,
1.0mmol) in THF (5 mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
diethyl ether 2:1) gave the title compound as a dark red solid (538 mg,
0.89 mmol, 89%). 1H NMR (300 MHz, C6D6): d ˆ 1.13 (s, 9H), 1.20(s, 9H),
4.46 (s, 1H), 5.06 (d, J ˆ 12.1 Hz, 1H), 5.10(s, 1H), 5.17 (d, J ˆ 12.1 Hz,
1H), 7.05 7.27 (m, 6H), 7.34 7.41 (m, 2H), 7.46 7.51 (m, 2H); 13C NMR
(75 MHz, C6D6): d ˆ 29.83, 30.60, 66.84, 67.14, 67.62, 82.42, 85.39, 126.73,
128.06, 128.68, 128.75, 128.89, 129.35, 135.75, 146.06, 172.49; IR (KBr): nÄ ˆ
2972, 2362, 2337, 1751, 1734, 1456, 1367, 1190, 1159, 908, 895 cmÀ1; MS (EI):
Synthesis of bisimido osmium complex 2 and trisimido osmium complex 3
from monoimido osmium complex 1: A solution of 1 (1.6 g, 5.16 mmol) in
freshly distilled THF (10mL) was treated with N-trimethylsilyl tert-
butylamine (9.0mL, 47 mmol) and stirred under Ar at overnight. Standard
work-up and column chromatography as described above yielded
2
(530mg, 28%) and 3 (1.15 g, 53%).
Trioxo(N-tert-butylimido)osmium(viii) (1):[21, 29, 30] Yellow solid; 1H NMR
(300 MHz, C6D6): d ˆ 0.87 (s, 9H); 13C NMR (75 MHz, C6D6): d ˆ 27.42,
82.65.
‡
m/z (%): 604 (9) [M] , 469 (100), 413 (63), 357 (36); HRMS: calcd for
C24H32N2O4188Os: 600.1920, found: 600.1914; elemental analysis calcd (%)
for C24H32N2O4Os: C 47.82, H 5.35, N 4.65; found: C 48.09, H 5.61, N 4.91.
Dioxobis(N-tert-butylimido)osmium(viii) (2):[21, 29, 30] Orange solid;
1H NMR (300 MHz, C6D6): d ˆ 1.12 (s, 9H); 13C NMR (75 MHz, C6D6):
d ˆ 29.60, 75.23.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-methyl-5-(methyloxycarbonyl)-2-os-
ma(vi)imidazolidine (15): Obtained as described above from reaction
between methyl crotonate (120mg, 1.2 mmol) and complex 2 (364 mg,
1.0mmol) in THF (2 mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
diethyl ether 10:1) gave the title compound as a dark purple solid (424 mg,
0.91 mmol, 91%). 1H NMR (300 MHz, C6D6): d ˆ 0.90 (d, J ˆ 6.2 Hz, 3H),
1.14 (s, 9H), 1.19 (s, 9H), 3.29 (s, 3H), 3.86 (q, J ˆ 6.2 Hz, 1H), 3.87 (s, 1H);
13C NMR (75 MHz, C6D6): d ˆ 24.44, 29.93, 30.54, 51.48, 66.46, 66.64, 74.56,
81.99, 173.28; IR (KBr): nÄ ˆ 2976, 2362, 2337, 1751, 1365, 1196, 1176, 909,
Oxotris(N-tert-butylimido)osmium(viii) (3):[21, 29] Orange to red solid;
1H NMR (300 MHz, C6D6): d ˆ 1.24 (s, 9H); 13C NMR (75 MHz, C6D6):
d ˆ 30.06, 71.50.
Methyl 3-(3'-pyridinyl) acrylate (11):
A solution of thionyl chloride
(2.0mL, 27 mmol) in freshly destilled absolute methanol (15 mL) was
stirred under Ar at 08C. 3-(3'-Pyridinyl) acrylic acid (2.0g, 13.4 mmol) was
added in small portions and the resulting reaction mixture was stirred
overnight at room temperature. It was evaporated under reduced pressure
to a volume of about 3 mL, diluted with dichloromethane and washed with
a saturated solution of ammonium chloride. The organic phase was
separated, dried over MgSO4 and evaporated to leave the title compound
as a colourless solid (2.14 g, 98%). 1H NMR (300 MHz, CDCl3): d ˆ 3.74 (s,
3H), 6.44(d, J ˆ 16.0Hz, 1H), 7.27 (dd, J ˆ 4.7, 8.1 Hz, 1H), 7.60(d, J ˆ
16.0Hz, 1H), 7.77 (dt ps, J ˆ 1.7, 8.1 Hz, 1H), 8.53 (dd, J ˆ 1.2, 4.7 Hz, 1H),
8.67 (d, J ˆ 1.3 Hz, 1H); 13C NMR (75 MHz, CDCl3): d ˆ 51.71, 120.09,
123.69, 130.17, 134.35, 140.78, 149.21, 150.50, 166.46.
887 cmÀ1; MS (EI): m/z (%): 466 (16) [M] , 451 (24), 407 (33), 351 (55), 295
‡
(36), 84 (37), 57 (100); HRMS: calcd for C13H26N2O4188Os: 462.1452; found:
462.1456.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-methyl-5-(ethyloxycarbonyl)-2-os-
ma(vi)imidazolidine (16): Obtained as described above from reaction
between ethyl crotonate (137 mg, 1.2 mmol) and complex 2 (364 mg,
1.0mmol) in THF (2 mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
diethyl ether 10:1) gave the title compound as a deep red to purple solid
(442 mg, 0.92 mmol, 92%). 1H NMR (300 MHz, C6D6): d ˆ 0.91 (d, J ˆ
6.0Hz, 3H), 0.99 (t, J ˆ 7.1 Hz, 3H), 1.16 (s, 9H), 1.22 (s, 9H), 3.85 (q, J ˆ
7.1 Hz, 2H), 3.87 (s, 1H), 3.91 (q, J ˆ 6.0Hz, 1H); 13C NMR (75 MHz,
C6D6): d ˆ 14.04, 24.46, 29.99, 30.57, 61.08, 66.45, 66.53, 74.57, 82.07, 172.88;
IR (KBr): nÄ ˆ 2966, 2362, 2330, 1748, 1349, 1190, 1119, 910, 885 cmÀ1; MS
General procedure for diamination of achiral olefins with osmium bisimido
complex 2: Solid bisimido osmium complex 2 was added in one portion to a
solution of the appropriate olefin (1.2 mmol) in freshly distilled THF and
the resulting solution was stirred at room temperature overnight (approx.
12 h). The solvent was evaporated under reduced pressure and the
remaining crude oily residue was analysed by NMR. The pure product
was obtained by column chromatography as indicated for the individual
compound.
‡
(EI): m/z (%): 480(8) [ M] , 465 (9), 407 (28), 351 (41), 295 (22), 84 (42), 57
(100); HRMS: calcd for C14H28N2O4188Os: 476.1608, found: 476.1603.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(methyloxycarbonyl)-2-os-
ma(vi)imidazolidine (12): Obtained as described above from reaction
between methyl cinnamate (194 mg, 1.2 mmol) and complex 2 (346 mg,
1.0mmol) in THF (3 mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
n-hexane 1:1) gave the title compound as an orange-to-red solid (496 mg,
0.94 mmol, 94%). 1H NMR (500 MHz, C6D6): d ˆ 1.06 (s, 9H), 1.17 (s, 9H),
3.36 (s, 3H), 4.35 (s, 1H), 4.97 (s, 1H), 6.97 7.01 (m, 1H), 7.05 7.10 (m,
2H), 7.28 7.32 (m, 2H); 13C NMR (125 MHz, C6D6): d ˆ 29.77, 30.60, 51.67,
66.79, 67.66, 82.32, 85.24, 126.71, 128.29, 128.85, 146.08, 173.26; IR (KBr):
nÄ ˆ 2980, 1749, 1468, 1454, 1369, 1196, 1169, 999, 904, 887 cmÀ1; MS (EI):
trans-1,3-Bis(tert-butyl)-2,2-dioxo-5-(methyloxycarbonyl)-2-osma(vi)imi-
dazolidine (17): Obtained as described above from reaction between
methyl acrylate (50 mL, 0.58 mmol) and complex 2 (177 mg, 0.48 mmol) in
THF (1.5 mL). Evaporation of the solvent under reduced pressure followed
by column chromatography (silica gel, dichloromethane/n-hexane 1:1) gave
the title compound as a red solid (213 mg, 0.47 mmol, 98%). 1H NMR
(300 MHz, C6D6): d ˆ 1.14 (s, 9H), 1.24 (s, 9H), 3.27 (s, 3H), 3.35 (dd, J ˆ
0.75 Hz, J ˆ 12.4 Hz, 1H), 3.46 (dd, J ˆ 6.6 Hz, J ˆ 12.4 Hz, 1H), 4.14 (dd,
J ˆ 0.75 Hz, J ˆ 6.6 Hz, 1H); 13C NMR (75 MHz, C6D6): d ˆ 29.34, 29.82,
51.60, 66.63, 66.79, 68.80, 75.19, 173.64; IR (KBr): nÄ ˆ 2970, 1751, 1734,
1466, 1367, 1188, 1169, 1111, 1038, 1014, 1001, 891 cmÀ1; MS (EI): m/z (%):
5590
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2003, 9, 5581 5596

Diamination of Olefins
5581 5596
‡
450(27) [ M] , 437 (28), 393 (100), 337 (42), 281 (53); HRMS: calcd for
(%) for C16H33N3O3Os: C 38.00, H 6.58, N 8.31; found: C 37.68, H 6.65, N
8.22.
C12H24N2O4188Os: 448.1295, found: 448.1303.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-5-(N-tert-butylaminocarbonyl)-2-os-
ma(vi)imidazolidine (30): Obtained as described above from reaction
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4,5-bis(methyloxycarbonyl)-2-osma-
(vi)imidazolidine (18):[21] Obtained as described above from reaction
between dimethyl fumarate (173 mg, 1.2 mmol) and complex 2 (364 mg,
1.0mmol) in THF (4 mL). Evaporation of the solvent under reduced
pressure followed by column chromatography (silica gel, dichloromethane/
n-hexane 4:1) gave the title compound as a red solid (457 mg, 0.9 mmol,
90%). 1H NMR (300 MHz, C6D6): d ˆ 1.16 (s, 18H), 3.30(s, 6H), 4.50(s,
2H); 13C NMR (75 MHz, C6D6): d ˆ 29.85, 52.02, 66.70, 80.55, 172.20; IR
(KBr): nÄ ˆ 2960, 1743, 1432, 1365, 1207, 1117, 937, 922 cmÀ1; MS (EI): m/z
between N-tert-butyl acrylamide (120mg, 0.94 mmol) and complex
2
(287 mg, 0.79 mmol) in THF (1 mL). Evaporation of the solvent under
reduced pressure followed by column chromatography (silica gel, n-
hexane/ethyl acetate 4:1) gave the title compound as a bright red solid
(345 mg, 0.70 mmol, 89%). 1H NMR (300 MHz, C6D6): d ˆ 0.82 (s, 9H),
0.95 (s, 9H), 1.04 (s, 9H), 3.19 3.26 (m, 2H), 3.34 (dd, J ˆ 0.8, 12.2 Hz,
1H), 3.85 (dd, J ˆ 0.8, 6.4 Hz, 1H); 13C NMR (75 MHz, C6D6): d ˆ 28.68,
29.18, 29.81, 50.82, 51.21, 53.26, 66.86, 67.48, 169.98; IR (KBr): nÄ ˆ 3388,
3265, 3068, 2970, 2362, 2337, 1670, 1625, 1551, 1458, 1363, 1220, 982, 908,
‡
(%): 510(9) [ M] , 495 (28), 451 (100), 395 (33), 339 (66).
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-(3'-pyridinyl)-5-(methyloxycarbonyl)-
2-osma(vi)imidazolidine (19): Obtained as described above from reaction
between methyl 3-(3'-pyridinyl)acrylate (106 mg, 0.65 mmol) and complex
2 (200 mg, 0.54 mmol) in freshly distilled THF (3 mL). Evaporation of the
solvent under reduced pressure followed by column chromatography (silica
gel, dichloromethane/diethyl ether 10:1) gave the title compound as a
bright red solid (222 mg, 0.42 mmol, 78%). 1H NMR (300 MHz, C6D6): d ˆ
1.01 (s, 9H), 1.08 (s, 9H), 3.32 (s, 3H), 4.19 (s, 1H), 4.87 (s, 1H), 6.68 (dd,
J ˆ 4.7, 8.0Hz, 1H), 7.59 (dt ps, J ˆ 1.7, 8.0Hz, 1H), 8.41 (dd, J ˆ 1.9, 4.7 Hz,
1H), 8.66 (d, J ˆ 2.0Hz, 1H); 13C NMR (75 MHz, C6D6): d ˆ 29.73, 30.56,
51.84, 66.75, 67.58, 79.72, 84.79, 123.37, 133.10, 141.26, 149.24, 149.81, 172.72;
IR (KBr): nÄ ˆ 3003, 2972, 2968, 2355, 2339, 1755, 1463, 1366, 1194, 902,
‡
887 cmÀ1; MS (EI): m/z (%): 493 (2) [M] , 394 (54), 337 (40), 57 (100);
HRMS: calcd for C15H31N3O3188Os: 489.1924, found: 489.1931; elemental
analysis calcd (%) for C15H31N3O3Os: C 36.64, H 6.36, N 8.55; found: C
36.33, H 6.61, N 8.44.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(N-methoxy,N-methyl-ami-
nocarbonyl)-2-osma(vi)imidazolidine (31): Obtained as described above
from reaction between N-methoxy,N-methyl-cinnamoylamide (100 mg,
0.52 mmol) and complex 2 (159 mg, 0.44 mmol) in THF (3 mL). Evapo-
ration of the solvent under reduced pressure followed by column
chromatography (silica gel, n-hexanes/ethyl acetate 2:1) gave the title
compound as a red oily solid (203 mg, 0.37 mmol, 84%). 1H NMR
(300 MHz, C6D6): d ˆ 1.24 (s, 9H), 1.25 (s, 9H), 2.81 (s, 3H), 3.05 (s, 3H),
4.71 (s, 1H), 4.96 (S, 1H), 7.01 7.17 (m, 3H), 7.43 7.48 (m, 2H); 13C NMR
(75 MHz, C6D6): d ˆ 30.30, 30.90, 33.11, 60.67, 66.80, 67.72, 81.35, 82.21,
126.86, 127.79, 128.11, 128.76, 146.99, 174.10; IR (KBr): nÄ ˆ 2972, 2933,
2362, 2337, 1676, 1464, 1367, 1190, 909, 903 cmÀ1; MS (EI): m/z (%): 557 (3)
‡
891 cmÀ1; MS (EI): m/z (%): 528 (4) [M] , 478 (22), 414 (24), 358 (14), 147
(28), 105 (61), 57 (100); HRMS: calcd for C17H27N3O4188Os: 525.1558,
found: 525.1553.
Competition experiment for diamination with bisimido complex 2: A
solution of methyl cinnamate (162 mg, 1 mmol) and dimethyl fumarate
(144 mg, 1 mmol) in C6D6 (3 mL) under Ar was treated with complex 2
(364 mg, 1 mmol) and stirred at RT. The reaction was monitored by
1H NMR with samples being taken every 60min and the reaction outcome
was determined by comparison of the integrals of the respective signals in
‡
[M] , 469 (40), 413 (62), 357 (44), 146 (33), 105 (31), 57 (100); HRMS: calcd
for C19H31N3O4188Os: 553.1872, found: 553.1883; elemental analysis calcd
(%) for C19H31N3O4Os: C 41.07, H 5.62, N 7.56; found: C 41.00, H 5.79, N
7.22.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(phenylcarbonyl)-2-osma-
(vi)imidazolidine (32): Obtained as described above from reaction between
chalcone (125 mg, 0.6 mmol) and complex 2 (183 mg, 0.5 mmol) in THF
(4 mL). Evaporation of the solvent under reduced pressure followed by
column chromatography (silica gel, dichloromethane/n-hexane 4:1) gave
the title compound as a bright red solid (260mg, 0.45 mmol, 91%).
1H NMR (300 MHz, C6D6): d ˆ 1.00 (s, 9H), 1.03 (s, 9H), 4.68 (s, 1H), 5.26
(s, 1H), 6.90 7.11 (m, 6H), 7.18 7.25 (m, 2H), 7.80 7.85 (m, 2H);
13C NMR (75 MHz, C6D6): d ˆ 30.39, 30.80, 88.78, 67.56, 81.20, 85.89,
126.75, 128.20, 128.59, 129,13, 129.37, 133.61, 136.00, 146.43, 196.76; IR
(KBr): nÄ ˆ 2972, 1689, 1450, 1369, 1212, 1184, 970, 901, 894 cmÀ1; MS (EI):
1
the H NMR spectra.
cis-1,3-Bis(tert-butyl)-2,2-dioxo-4,5-bis(methyloxycarbonyl)-2-osma(vi)-
imidazolidine (21): A solution of dimethyl maleic ester (72 mg, 0.5 mmol)
in THF (5 mL) was treated with complex 2 (91 mg, 0.25 mmol) and stirred
for 14 h at RT. The solvent was removed under reduced pressure. Analysis
by 1H NMR showed a ratio of 1.3:1 for the title compound and 18. Column
chromatography (silica gel, n-hexane/ethyl acetate 4:1) gave a red solid
material (136 mg, 0.21 mmol, 84%) which was analysed by 1H NMR to
consist of a 1:1.7 mixture of the title compound and 18. Data for 21:
1H NMR (300 MHz, C6D6): d ˆ 0,97 (s, 18H), 3.07 (s, 6H), 4.42 (s, 2H).
‡
m/z (%): 573 [M] , 496 (53), 393 (47), 146 (29), 195 (25), 57 (100);
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-(N-tert-butylaminocarbon-
yl)-2-osma(vi)imidazolidine (28): Obtained as described above from
reaction between N-tert-butyl cinnamoyl amide (244 mg, 1.2 mmol) and
complex 2 (364 mg, 1.0mmol) in THF (3 mL). Evaporation of the solvent
under reduced pressure followed by column chromatography (silica gel n-
hexane/ethyl acetate 4:1) gave the title compound as a bright red solid
(506 mg, 0.89 mmol, 89%). 1H NMR (300 MHz, C6D6): d ˆ 1.02 (s, 9H),
1.15 (s, 9H), 1.37 (s, 9H), 4.31 (s, 1H), 5.25 (s, 1H), 5.77 (brs, 1H), 6.92
7.01 (m, 1H), 7.02 7.10 (m, 2H), 7.31 7.40 (m, 2H); 13C NMR (75 MHz,
C6D6): d ˆ 28.70, 29.77, 30.40, 51.48, 67.45, 67.96, 83.23, 87.66, 127.87, 128.17,
128.82, 146.28, 171.82; IR (KBr): nÄ ˆ2976, 1674, 1515, 1456, 1394, 1369,
elemental analysis calcd (%) for C23H30N2O3Os: C 48.23, H 5.28, N 4.89;
found: C 48.08, H 5.33, N 4.77.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-formyl-2-osma(vi)imidazoli-
dine (33): Obtained as described above from reaction between cinnamic
aldehyde (146 mg, 1.2 mmol) and complex 2 (364 mg, 1.0mmol) in THF
(5 mL). Evaporation of the solvent under reduced pressure followed by
column chromatography (silica gel, dichloromethane/diethyl ether 10:1)
gave the title compound as a dark red solid (527 mg, 0.92 mmol, 92%).
1H NMR (300 MHz, C6D6): d ˆ 0.94 (s, 9H), 1.09 (s, 9H), 3.86 (d, J ˆ
3.0Hz, 1H), 4.89 (s, 1H), 6.94 7.07 (m, 5H), 9.26 (d, J ˆ 3.0Hz, 1H);
13C NMR (75 MHz, C6D6): d ˆ 30.12, 30.46, 66.89, 67.88, 80.57, 89.20, 126.85,
128.08, 128.86, 144.82, 201.47; IR (KBr): nÄ ˆ 2976, 1731, 1464, 1366, 1184,
‡
1311, 1242, 1184, 995, 983, 901, 891 cmÀ1; MS (EI): m/z (%): 569 (4) [M] ,
469 (94), 413 (100), 357 (46), 310 (19); HRMS: calcd for C21H35N3O3188Os:
565.2237, found: 565.2242.
‡
897 cmÀ1; MS (EI): m/z (%): 469 (51) [M À CHO] , 413 (72), 357 (64), 146
(43), 57 (100); HRMS: calcd for C17H26N2O3188Os: 494.1499, found:
494.1495; elemental analysis calcd (%) for C17H26N2O3Os: C 41.11, H
5.28, N 5.64; found: C 41.00, H 5.71, N 5.67.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-methyl-5-(N-tert-butylaminocarbon-
yl)-2-osma(vi)imidazolidine (29): Obtained as described above from
reaction between N-tert-butyl crotyl amide (141 mg, 1.0mmol) and
complex 2 (303 mg, 0.83 mmol) in THF (2 mL). Evaporation of the solvent
under reduced pressure followed by column chromatography (silica gel n-
hexane/ethyl acetate 4:1) gave the title compound as a bright red solid
(362 mg, 0.72 mmol, 86%). 1H NMR (300 MHz, C6D6): d ˆ 0.90 (d, J ˆ
6.2 Hz, 3H), 1.11 (s, 9H), 1.16 (s, 9H), 1.31 (s, 9H), 3.85 (s, 1H), 4.12 (q, J ˆ
6.2 Hz, 3H), 4.59 4.65 (brs, 1H); 13C NMR (75 MHz, C6D6): d ˆ 14.16,
28.64, 29.92, 30.30, 50.66, 51.28, 67.09, 164.53; IR (KBr): nÄ ˆ 2970, 2927,
2362, 2333, 1674, 1653, 1456, 1367, 1190, 906, 885 cmÀ1; MS (EI): m/z (%):
trans-1,3-Bis(tert-butyl)-2,2-dioxo-5-cyano-2-osma(vi)imidazolidine (35):
Obtained as described above from reaction between acrylonitrile (50 mL,
0.75 mmol) and complex 2 (92 mg, 0.25 mmol) in THF (1 mL). Evaporation
of the solvent under reduced pressure followed by column chromatography
(silica gel n-hexane/ethyl acetate 4:1) gave the title compound as a bright
red, air-sensitive solid (79 mg, 0.19 mmol, 76%). 1H NMR (300 MHz,
C6D6): d ˆ 1.17 (s, 9H), 1.22 (s, 9H), 3.30(dd, J ˆ 0.78 Hz, J ˆ 11.9 Hz, 1H),
3.46 (dd, J ˆ 6.7 Hz, J ˆ 11.9 Hz, 1H), 4.14 (dd, J ˆ 0.78 Hz, J ˆ 6.7 Hz,
1H); 13C NMR (75 MHz, C6D6): d ˆ 29.03, 29.58, 52.53, 64.30, 65.81, 67.78,
‡
507 (9) [M] , 451 (45), 352 (61), 296 (22), 57 (100); elemental analysis calcd
Chem. Eur. J. 2003, 9, 5581 5596
www.chemeurj.org
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5591

ƒ
K. Muniz et al.
FULL PAPER
169.68; IR (KBr): nÄ ˆ 3021, 2965, 1751, 1442, 1295, 1182, 894, 704 cmÀ1; MS
worked-up and purified any further, and a representative example is given
below for the diamination of (À)-8-phenyl menthyl cinnamate.
‡
(EI): m/z (%): 418 (8) [M] , 393 (100), 337 (32), 281 (45); HRMS: calcd for
C11H21N3O2188Os: 415.1191, found: 415.1189.
Synthesis of 8-phenyl menthyl cinnamate (41d):[74] DMAP (672 mg,
5.5 mmol) was added in one portion at 08C to a solution of cinnamoyl
chloride (830mg, 5 mmol) in freshly distilled THF (30mL). An immediate
precipitate was observed and the resulting inhomogeneous solution was
stirred for 15 min before a solution of 8-phenyl menthol (1.16 g, 5 mmol) in
dichloromethane (5 mL) was added. The resulting solution was allowed to
warm to room temperature and stirred overnight. The solvent was removed
under reduced pressure and the crude product was purified by column
chromatograpy (silica gel, hexanes/ethyl acetate 15:1) to give the title
compound as a white solid (1.1 g, 61%). 1H NMR (300 MHz, C6D6): d ˆ
0.74 1.10 (m, 3H), 0.80 (d, J ˆ 6.6 Hz, 3H), 1.15 (s, 3H), 1.25 (s, 3H), 1.35
1.75 (m, 3H), 1.80 1.93 (m, 1H), 1.96 2.10 (m, 1H), 4.83 (dt, J ˆ 4.4,
10.8 Hz, 1H), 5.69 (d, J ˆ 16.0, 1H), 6.96 7.33 (m, 11H); 13C NMR
(75 MHz, C6D6): d ˆ 21.77, 24.28, 26.50, 28.42, 31.28, 34.63, 39.58, 50.68,
74.28, 118.77, 124.73, 125.41, 127.92, 127.96, 128.68, 129.86, 134.57, 143.54,
151.79, 166.00.
trans-1,3-Bis(tert-butyl)-2-oxo-2-tert-butylimido-4,5-bis(methyloxycarbon-
yl)-2-osma(vi)imidazolidine (36):[21] Obtained as described above from
reaction between dimethyl fumarate (86 mg, 0.6 mmol) and complex 3
(210mg, 0.5 mmol) in THF (2 mL). Evaporation of the solvent under
reduced pressure followed by column chromatography (silica gel, dichloro-
methane/ethyl acetate 10:1) gave the title compound as deep red solid
(260mg, 0.46 mmol, 92%). 1H NMR (300 MHz, C6D6): d ˆ 1.27 (s, 9H),
1.28 (s, 9H), 1.49 (s, 9H), 3.22 (s, 3H), 3.41 s, 3H), 4.56 (s, 3H), 4.58 (s, 3H);
13C NMR (75 MHz, C6D6): d ˆ 30.31, 31.35, 31.69, 51.64, 51.68, 63.66, 64.17,
‡
69.33, 80.56, 81.96, 173.39, 173.97; MS (EI): m/z (%): 565 (22) [M] , 550
(22), 506 (100), 394 (20); HRMS: calcd for C18H35N3O5188Os: 561.2135,
found: 561.2132; analytical HPLC: Daicel Chiralpak AS, 254 nm, n-
hexane/2-propanol 98:2, 0.5 mLminÀ1; tR ˆ 13.4 min [(‡)-36], 15.4 min
[(À)-36].
trans-1,3-Bis(tert-butyl)-2-oxo-2-tert-butylimido-4,5-bis(ethyloxycarbon-
yl)-2-osma(vi)imidazolidine (38): Obtained as described above from
reaction between diethyl fumarate (103 mg, 0.6 mmol) and complex 3
(210mg, 0.5 mmol) in THF (2 mL). Evaporation of the solvent under
reduced pressure followed by column chromatography (silica gel, dichloro-
methane/ethyl acetate 10:1) gave the title compound as deep red solid
(270mg, 0.46 mmol, 91%). 1H NMR (300 MHz, C6D6): d ˆ 0.90 (t, J ˆ
7.2 Hz, 3H), 1.08 (t, J ˆ 7.2 Hz, 3H), 1.31 (s, 9H), 1.34 (s, 9H), 1.51 (s, 9H),
3.84 (q, J ˆ 7.2 Hz, 2H), 4.01 (q, J ˆ 7.2 Hz, 2H), 4.59 (d, J ˆ 0.6 Hz, 1H),
4.63 (d, J ˆ 0.6 Hz, 1H); 13C NMR (75 MHz, C6D6): d ˆ 14.48, 14.50, 30.68,
31.81, 32.16, 61.29, 61.55, 63.97, 64.47, 69.59, 80.93, 82.41, 173.30, 173.90; IR
(KBr): nÄ ˆ 2972, 2935, 2904, 2870, 1751, 1464, 1365, 1234, 1200, 1108, 962,
Asymmetric diamination of 8-phenyl menthyl cinnamate 41d: (À)-8-
Phenyl menthyl cinnamate (181 mg, 0.5 mmol) was added to a solution of
bis(N-tert-butylimido)dioxoosmium(viii) (2) (183 mg, 0.5 mmol) in freshly
distilled THF (5 mL). The resulting orange solution was stirred at RT for
8 h during which it turned dark red. The solvent was removed under
reduced pressure to leave a red-brown oil which was passed through a small
pad of silica gel (hexanes/ethyl acetate 4:1). After evaporation of the
solvents under reduced pressure, the pure mixture of the two diastereomers
(248 mg, 0.34 mmol, 68% yield) was separated by semipreparative HPLC
(Knauer Eurospher 100CN, tBuOCH3/n-hexane 15:85, 14 mLminÀ1
254 nm). tR ˆ 12.9 min for 43d and 15.6 min for 42d; analytical HPLC:
Knauer Eurospher 100CN, tBuOCH3/n-hexane 20:80, 1.0 mLmin À1
,
‡
893 cmÀ1; MS (EI): m/z (%): 593 (17) [M] , 520 (100), 464 (39), 408 (36), 72
,
(28), 57 (67); HRMS: calcd for C20H39N3O5188Os: 589.2448, found:
589.2450.
254 nm, tR ˆ 7.4 min [(‡)-43d], 8.8 min [(À)-42d].
(4R,5S)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-[(À)-(8-phenyl-
menthyloxy)carbonyl]-2-osma(vi)imidazolidine (42d): Obtained as a pur-
Dihydroxylation/aminohydroxylation of dimethyl fumarate (10) with
monoimido complex 1: Solid monoimido complex 1 (309 mg, 1 mmol)
was added in one portion to a solution of dimethyl fumarate (290mg,
2 mmol) in freshly distilled THF (5 mL) and the resulting solution was
stirred at room temperature overnight and then treated with a saturated
solution of sodium bisulfite. The aqueous layer was extracted with
dichloromethane, dried over MgSO4 and evaporated under reduced
pressure. The crude product as analysed by NMR to indicate unreacted
starting material, dimethyl tartrate 39 and the monoaza analogue 40.
Purification by column chromatography (dichloromethane/ethyl acetate
4:1) gave 39 as first, and 40 as second fraction.
1
ple solid; [a]2D8 ˆ À 1922 (c ˆ 0.15); H NMR (300 MHz, C6D6): d ˆ 0.47
1.39 (m, 6H), 0.71 (d, J ˆ 6.6 Hz, 3H), 1.16 (s, 9H), 1.29 (s, 3H), 1.34 (s, 9H),
1.58 (s, 3H), 1.85 1.99 (m, 1H), 2.01 2.12 (m, 1H), 4.32 (s, 1H), 5.02 (dt,
J ˆ 4.3, 10.5 Hz, 1H), 5.21 (s, 1H), 7.00 7.28 (m, 9H), 7.40 7.46 (m, 1H);
13C NMR (75 MHz, C6D6): d ˆ 21.81, 23.97, 27.75, 30.23, 30.95, 31.37, 31.39,
34.56, 40.71, 41.55, 50.59, 66.84, 67.83, 76.72, 81.73, 85.03, 125.99, 127.02,
128.17, 128.52, 128.91, 146, 08, 150.42, 171.73; IR (KBr): nÄ ˆ 2972, 2950,
2868, 1730, 1367, 1194, 912, 885, 768, 700 cmÀ1; MS (EI): m/z (%): 728 (2)
‡
[M] , 469 (17), 413 (8), 279 (15), 146 (100); HRMS: calcd for
C33H48N2O4188Os: 724.3172, found: 724.3161.
Dimethyl tartrate (39): 1H NMR (300 MHz, CDCl3): d ˆ 3.85 (s, 6H), 4.55
(4S,5R)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-phenyl-5-[(À)-(8-phenyl-
menthyloxy)carbonyl]-2-osma(vi)imidazolidine (43d): Obtained as a pur-
ple solid. [a]2D8 ˆ ‡ 1110( c ˆ 0.12); 1H NMR (300 MHz, C6D6): d ˆ 0.79 (d,
J ˆ 6.4 Hz, 3H), 0.80 0.95 (m, 4H), 1.08 (s, 3H), 1.18 (s, 9H), 1.19 (s, 9H),
1.22 (s, 3H), 1.43 1.55 (m, 1H), 1.60 1.71 (m, 1H), 2.05 2.20 (m, 2H),
3.64 (s, 1H), 4.77 (dt, J ˆ 4.1, 10.7 Hz, 1H), 4.90 (s, 1H), 6.85 6.93 (m, 1H),
7.01 7.28 (m, 9H); 13C NMR (75 MHz, C6D6): d ˆ 21.85, 23.77, 26.74, 29.44,
30.23, 30.93, 31.28, 34.81, 39.49, 41.80, 50.19, 66.81, 67.44, 76.35, 81.31, 84.11,
125.41, 125.69, 127.18, 127.67, 127.90, 128.31, 128.63, 171.23; IR (KBr): nÄ ˆ
2970, 2927, 2870, 1741, 1367, 1192, 1169, 913, 901, 700 cmÀ1; MS (EI): m/z
(s, 2H); 13C NMR (75 MHz, CDCl3): d ˆ 53.08, 72.00, 171.89.
Dimethyl 2-hydroxy-3-(N-tert-butyl)amino succinate (40): 1H NMR
(300 MHz, CDCl3): d ˆ 1.04 (s, 9H), 3.28 3.42 (brs, 2H), 3.77 (s, 3H),
3.78 (s, 3H), 3.84 (d, J ˆ 3.4 Hz, 1H), 4.42 (d, J ˆ 3.4 Hz, 1H); 13C NMR
(75 MHz, CDCl3): d ˆ 28.71, 51.73, 52.44, 52.75, 57.58, 72.38, 172.13, 173.11;
IR (KBr): nÄ ˆ 3012, 2976, 2970, 1783, 1764, 1127, 1008, 989 cmÀ1; MS (EI):
‡
m/z (%): 234 (21) [M] , 178 (100), 162 (35), 122 (41); HRMS: calcd for
C10H19NO5: 233.1263, found: 233.1261; elemental analysis calcd (%) for
C10H19NO5: C 51.49, H 8.21, N 6.00; found: C 51.33, H 8.59, N 6.23.
‡
(%): 728 (2) [M] , 469 (17), 413 (11), 279 (39), 146 (100); HRMS: calcd for
C33H48N2O4188Os: 724.3172, found: 724.3166.
Competitive bisfunctionalisation of dimethyl fumarate (Figure 5): To a
solution of dimethyl fumarate (722 mg, 5 mmol) in freshly distilled THF
Synthesis of 8-phenyl menthyl crotylate (44): To a solution of crotyl
chloride (462 mg, 3 mmol) in freshly distilled THF (30mL) at 0 8C was
added DMAP (403 mg, 3.3 mmol) in one portion. An immediate precip-
itate was observed and the resulting inhomogeneous solution was stirred
for 15 min before a solution of 8-phenyl menthol (697 mg, 3 mmol) in
dichloromethane (5 mL) was added. The resulting solution was allowed to
warm to room temperature and stirred overnight. The solvent was removed
under reduced pressure and the crude product was purified by column
chromatograpy (silica gel, hexanes/ethyl acetate 12:1) to give the title
compound as a white solid (0.488 g, 54%). 1H NMR (300 MHz, CDCl3):
d ˆ 0.71 1.17 (m, 3H), 0.76 (d, J ˆ 6.6 Hz, 3H), 1.12 (s, 3H), 1.21 (s, 3H),
1.32 1.41 (m, 1H), 1.61 (dd, J ˆ 1.7, 7.0Hz, 3H), 1.79 1.86 (m, 1H), 1.90
1.98 (m, 1H), 4.83 (dt, J ˆ 4.4, 10.6 Hz, 1H), 5.24 (dd, J ˆ 1.7, 15.5 Hz, 1H),
6.35 (ddd, J ˆ 1.7, 7.0, 15.5 Hz, 1H), 6.98 7.03 (m, 2H), 7.11 7.19 (m, 3H);
13C NMR (75 MHz, CDCl3): d ˆ 17.61, 21.70, 25.25, 26.57, 27.52, 31.19, 34.56,
(5 mL) were added subsequentely monoimido complex
1 (155 mg,
0.5 mmol), bisimido complex 2 (182 mg, 0.5 mmol) and trisimido complex
3 (210mg, 0.5 mmol) and the resulting solution was stirred at room
temperature. Every 120min, samples were taken from this solution and
treated with a saturated solution of sodium bisulfite. Extraction with
dichloromethane, drying over MgSO4 and evaporation of the organic
solvent under reduced pressure gave a crude product. This was analysed by
1H NMR to determine the ratio of unreacted starting material, 12, 18 and
39. Formation of 40 was below detection level.
Screening of chiral auxiliaries for diastereoselective diamination with
complex 2: In these cases, diamination was carried out as described above
for the achiral substrates and the diastereomeric ratio of the crude product
mixture was estimated from a comparison of the hydrogen signals at C-4
and C-5 of the osmaimidazolidines. Generally, these reactions were not
5592
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2003, 9, 5581 5596

Diamination of Olefins
5581 5596
39.62, 41.68, 50.52, 73.92, 123.09, 124.64, 125.34, 127.82, 143.54, 151.54,
165.48.
(5S)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-5-[(À)-(8-phenyl-menthyloxy)car-
bonyl]-2-osma(vi)imidazolidine (48): Obtained as a red to purple solid;
[a]2D8 ˆ À956 (c ˆ 0.13); 1H NMR (300 MHz, C6D6): d ˆ 0.60 0.93 (m, 3H),
0.72 (d, J ˆ 6.4 Hz, 3H), 1.03 1.58 (m, 3H), 1.09 (s, 3H), 1.13 (s, 9H), 1.27
(s, 3H), 1.36 (s, 9H), 1.91 2.05 (m, 2H), 3.35 (dd, J ˆ 1.3, 12.0Hz, 1H), 3.41
(dd, J ˆ 6.0, 12.0 Hz, 1H), 3.60 (dd, J ˆ 1.3, 6.0Hz, 1H), 4.74 (dt, J ˆ 4.1,
10.6 Hz, 1H), 7.03 7.08 (m, 1H), 7.21 7.28 (m, 4H); 13C NMR (75 MHz,
C6D6): d ˆ 21.79, 25.13, 26.78, 28.20, 29.37, 30.16, 31.23, 34.75, 39.74, 41.82,
50.31, 66.46, 66.72, 67.85, 74.23, 76.04, 125.42, 125.69, 128.31, 152.34, 171.64;
IR (KBr): nÄ ˆ 2964, 2929, 2872, 1741, 1458, 1365, 1198, 1180, 908, 897,
Asymmetric diamination of 8-phenyl menthyl crotylate (44): (À)-8-Phenyl
menthyl crotylate (301 mg, 1.0 mmol) was added to a solution of 2 (182 mg,
0.5 mmol) in freshly distilled THF (5 mL). The resulting orange solution
was stirred at RT for 8 h during which it turned dark red. The solvent was
removed under reduced pressure to leave a crude red product which was
analysed by 1H NMR and then purified by column chromatography on
silica gel (hexanes/ethyl acetate 5:1). After evaporation of the solvents
under reduced pressure, the pure mixture of the two diastereomers
(270mg, 0.41 mmol, 81% yield) was separated by semipreparative HPLC
‡
706 cmÀ1; MS (EI): m/z (%): 652 (56) [M] , 393 (100), 337 (14), 281 (20),
119 (18); HRMS: calcd for C27H44N2O4188Os: 648.2859, found: 648.2857.
(Knauer Eurospher 100CN, tBuOCH3/n-hexane 15:85, 14 mLminÀ1
,
(5R)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-5-[(À)-(8-phenyl-menthyloxy)car-
254 nm). tR ˆ 17.5 min for 46 and 19.0min for 45; analytical HPLC: Knauer
Eurospher 100CN, tBuOCH3/n-hexane 20:80, 1.0 mLmin À1, 254 nm, tR
9.9 min [(‡)-46], 10.4 min [(À)-45].
bonyl]-2-osma(vi)imidazolidine (49): Obtained as a deep red solid; [a]D28
ˆ
1
‡710( c ˆ 0.04); H NMR (300 MHz, C6D6): d ˆ 0.59 0.75 (m, 2H), 0.73
(d, J ˆ 6.6 Hz, 3H), 0.80 0.91 (m, 2H), 1.08 (s, 3H), 1.10 1.18 (m, 2H),
1.23 (s, 9H), 1.26 (s, 3H), 1.30(s, 9H), 1.30 1.41 (m, 1H), 1.44 1.52 (m,
1H), 1.99 2.07 (m, 2H), 3.35 3.46 (m, 2H), 3.59 (dd, J ˆ 1.7, 5.5 Hz, 1H),
4.76 (dt, J ˆ 4.2, 10.7 Hz, 1H), 7.01 7.07 (m, 1H), 7.13 7.26 (m, 4H);
13C NMR (75 MHz, C6D6): d ˆ 21.86, 25.45, 26.86, 28.32, 29.62, 30.12, 31.28,
34.70, 39.77, 41.22, 49.80, 66.79, 66. 81, 69.01, 74.76, 75.98, 125.49, 125.68,
128.25, 151.96, 172.06; IR (KBr): nÄ ˆ 2968, 2929, 2870, 2362, 2337, 1738,
(4R,5S)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-methyl-5-[(À)-(8-phenyl-
menthyloxy)carbonyl]-2-osma(vi)imidazolidine (45): Obtained as a purple
solid. [a]2D8 ˆ À1676 (c ˆ 0.08); 1H NMR (300 MHz, C6D6): d ˆ 0.69 0.96
(m, 3H), 0.75 (d, J ˆ 6.4 Hz, 3H), 0.90 (d, J ˆ 6.2 Hz, 3H), 1.02 (s, 3H),
1.15 1.30(m, 1H), 1.16 (s, 9H), 1.18 (s, 3H), 1.34 (s, 9H), 1.43 1.49 (m,
1H), 1.57 1.65 (m, 1H), 1.99 2.08 m, 2H), 3.12 (s, 1H), 3.78 (q, J ˆ 6.2 Hz,
1H), 4.64 (dt, J ˆ 4.1, 10.7 Hz, 1H), 6.98 7.04 (m, 1H), 7.18 7.26 (m, 4H);
13C NMR (75 MHz, C6D6): d ˆ 21.85, 23.02, 24.41, 26.49, 29.89, 30.30, 30.74,
31.22, 34.84, 39.39, 41.84, 50.03, 66.27, 66.50, 73.53, 75.92, 80.86, 125.32,
125.53, 128.25, 152.84, 171.10. IR (KBr): nÄ ˆ 2968, 2941, 1734, 1365, 1203,
‡
1367, 1194, 1174, 912, 897, 768, 702 cmÀ1; MS (EI): m/z (%): 652 (4) [M] ,
393 (100), 337 (11), 281 (17), 119 (10); HRMS: calcd for C27H44N2O4188Os:
648.2859, found: 648.2860.
Representative procedure for aminolysis of 5-alkyloxycarbonyl osmaimi-
dazolidines with N-tert-butyl amine: A solution of complex 42d (365 mg,
0.5 mmol) in N-tert-butyl amine (20mL) was treated with zinc chloride
(0.13 mmol) under Ar. The Schlenk apparatus was sealed and heated to
708C for 24 h. After cooling to room temperature and standard work-up,
the remaining pink residue was purified by column chromatography (silica
gel, n-hexanes/ethyl acetate 4:1) to eluate remaining starting material.
Changing the eluents to n-hexanes/ethyl acetate 2:1) gave the desired
amide (4R,5S)-28 (191 mg, 0.34 mmol, 67%) that eluated as a red band.
NMR spectroscopic data for the obtained osmaimidazolidines were in
complete agreement with those of authentic samples from direct diamina-
tion.
‡
912, 897, 700 cmÀ1; MS (EI): m/z (%): 666 (9) [M] , 647 (19), 407 (100), 351
(52), 295 (23), 119 (20); HRMS: calcd for C28H46N2O4188Os: 662.3016,
found: 662.3010.
(4S,5R)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4-methyl-5-[(À)-8-(phenyl-
menthyloxy)carbonyl]-2-osma(vi)imidazolidine (46): Obtained as a red/
purple solid. [a]2D8 ˆ ‡1375 (c ˆ 0.06); 1H NMR (300 MHz, C6D6): d ˆ
0.65 0.93 (m, 3H), 0.74 (d, J ˆ 6.4 Hz, 3H), 0.91 (d, J ˆ 6.2 Hz, 3H), 1.07
(s, 3H), 1.19 (s, 9H), 1.21 1.52 (m, 3H), 1.30(s, 3H), 1.35 (s, 9H), 1.99
2.10(m, 2H), 3.49 (s, 1H), 3.76 (q, J ˆ 6.2 Hz, 1H), 4.82 (dt, J ˆ 4.1, 10.6 Hz,
1H), 7.00 7.09 (m, 1H), 7.14 7.28 (m, 4H); 13C NMR (75 MHz, C6D6): d ˆ
21.86, 22.98, 24.55, 25.87, 28.26, 30.23, 30.85, 31.89, 34.74, 39.87, 41.34, 49.46,
66.42, 66.72, 74.04, 75.91, 81.69, 125.60, 125.62, 128.11, 151.81, 171.51; IR
(KBr): nÄ ˆ 2972, 2926, 2868, 2362, 1337, 1738, 1367, 1196, 1174, 912, 894,
Asymmetric diamination of bis[(À)-menthyl] fumarate (50) with osmium
complex 2: Bis[(À)-menthyl] fumarate (235 mg, 0.6 mmol) was added to a
solution of bis (N-tert-butylimido)dioxoosmium(viii) (183 mg, 0.5 mmol) in
freshly distilled THF (5 mL). The resulting orange solution was stirred at
RT for 5 h during which it turned dark red. The solvent was removed under
reduced pressure to leave a red-brown oil which was analysed by 1H NMR
and the purified by column chromatography on silica gel (hexanes/ethyl
acetate 4:1). After evaporation of the solvents under reduced pressure, the
pure mixture of the two diastereomers (334 mg, 0.44 mmol, 88%) was
separated by semipreparative HPLC (Knauer Eurospher 100CN,
tBuOCH3/n-hexane 10:90, 14 mLmin À1, 254 nm). tR ˆ 11.1 min for 52 and
11.8 min for 51; analytical HPLC: Knauer Eurospher 100 CN, 254 nm,
‡
700 cmÀ1; MS (EI): m/z (%): 666 (11) [M] , 407 (100), 351 (44), 295 (21),
119 (17); HRMS: calcd for C28H46N2O4188Os: 662.3016, found: 662.3012.
Synthesis of 8-phenyl menthyl acrylate (47): DMAP (672 mg, 5.5 mmol)
was added in one portion to a solution of acrylic chloride (452 mg, 5 mmol)
in freshly distilled THF (30mL) at 0 8C. An immediate precipitate was
observed and the resulting inhomogeneous solution was stirred for 15 min
before a solution of 8-phenyl menthol (1.16 g, 5 mmol) in dichloromethane
(5 mL) was added. The resulting solution was allowed to warm to room
temperature and stirred overnight. The solvent was removed under
reduced pressure and the crude product was purified by column chroma-
tograpy (silica gel, hexanes/ethyl acetate 14:1) to give the title compound as
a white solid (0.673 g, 43%). 1H NMR (300 MHz, CDCl3): d ˆ 0.78 (d, J ˆ
6.6 Hz, 3H), 0.81 1.05 (m, 3H), 1.14 (s, 3H), 1.23 (s, 3H), 1.35 1.45 (m,
1H), 1.52 1.62 (m, 2H), 1.82 1.87 (m, 1H), 1.92 2.01 (m, 1H), 4.79 (dt,
J ˆ 4.3, 10.7 Hz, 1H), 5.45 5.55 (m, 2H), 5.91 (ddd, J ˆ 4.7, 9.4, 14.1 Hz,
1H), 7.00 7.02 (m, 2H), 7.12 7.19 (m, 3H); 13C NMR (75 MHz, CDCl3):
d ˆ 21.70, 25.35, 26.58, 27.46, 31.22, 34.53, 39.64, 41.59, 50.48, 74.44, 124.90,
125.31, 127.89, 128.86, 129.70, 151.40, 165.25.
n-hexane/tBuOCH3 90:10, 1.0 mLmin À1
[(‡)-51].
;
tR ˆ 7.7 min [(À)-52], 8.6 min
(4R,5R)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4,5-bis[(À)-menthyloxycar-
bonyl]-2-osma(vi)imidazolidine (51): Obtained as a dark orange solid;
[a]2D8 ˆ ‡663 (c ˆ 0.15); 1H NMR (300 MHz, C6D6): d ˆ 0.54 0.92 (m, 6H),
0.76 (d, J ˆ 9.0Hz, 6H), 0.79 (d, J ˆ 9.6 Hz, 6H), 0.94 1.20 (m, 4H), 1.32
1.49 (m, 6H), 1.35 (s, 18H), 1.96 2.15 (m, 4H), 4.82 (s, 2H), 4.85 (dt, J ˆ
4.5, 10.7 Hz, 2H); 13C NMR (75 MHz, C6D6): d ˆ 15.98, 20.96, 22.04, 23.14,
26.05, 30.12, 31.47, 34.11, 40.92, 46.93, 66.49, 76.10, 80.89, 171.81. IR (KBr):
nÄ ˆ 2981, 2935, 2317, 2303, 1736, 1326, 1149, 932, 704 cmÀ1; MS (EI): m/z
Asymmetric diamination of 8-phenyl menthyl acrylate (47): (À)-8-Phenyl
menthyl acrylate (286 mg, 1.0mmol) was added to a solution of 2 (183 mg,
0.5 mmol) in freshly distilled THF (5 mL). The resulting orange solution
was stirred at RT for 4 h during which it turned dark red. The solvent was
removed under reduced pressure to leave a red-brown oil which was
analysed by 1H NMR and then purified by column chromatography on
silica gel (hexanes/ethyl acetate 6:1). After evaporation of the solvents
under reduced pressure, the pure mixture of the two diastereomers
(313 mg, 0.48 mmol, 96% yield) was separated by semipreparative HPLC
‡
(%): 758 (7) [M] , 575 (100), 437 (14), 393 (31), 337 (10), 281 (10);
elemental analysis calcd (%) for C32H58N2O6Os: C 50.77, H 7.72, N 3.70;
found: C 50.42, H 7.61, N 3.88.
(4S,5S)-trans-1,3-Bis(tert-butyl)-2,2-dioxo-4,5-bis[(À)-menthyloxycarbon-
yl]-2-osma(vi)imidazolidine (52): Obtained as an orange solid; [a]D28
ˆ
À1308 (c ˆ 0.1); 1H NMR (300 MHz, C6D6): d ˆ 0.55 1.03 (m, 6H),
0.77(d, J ˆ 6.7 Hz, 6H), 0.80 (d, J ˆ 6.8 Hz,6H), 0.96 (d, J ˆ 7.0Hz, 6H),
1.08 1.56 (m, 8H), 1.35 (s, 18H), 2.03 2.11 (m, 2H), 2.14 2.24 (m, 2H),
4.68 (s, 2H), 4.74 (dt, J ˆ 4.3, 10.7H, 2H); 13C NMR (75 MHz, C6D6): d ˆ
16.21, 20.98, 22.07, 23.24, 26.26, 30.17, 31.43, 34.29, 40.76, 47.16, 66.88, 76.16,
81.91, 171.62; IR (KBr): nÄ ˆ 2965, 2941, 2316, 1739, 1361, 1159, 911,
(Knauer Eurospher 100CN, tBuOCH3/n-hexane 20:80, 14 mLmin À1
,
254 nm); tR ˆ 13.4 min for 49 and 15.0min for 48; analytical HPLC:
Knauer Eurospher 100 CN, 254 nm, n-hexane/tBuOCH3 80:20,
1.0mLmin À1, tR ˆ 10.0 min [(À)-48], 11.4 min [(‡)-49].
Chem. Eur. J. 2003, 9, 5581 5596
www.chemeurj.org
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5593

ƒ
K. Muniz et al.
FULL PAPER
‡
701 cmÀ1; MS (EI): m/z (%): 758 (7) [M] , 575 (100), 437 (12), 393 (34), 337
(13), 281 (9); elemental analysis calcd (%) for C32H58N2O6Os: C 50.77, H
7.72, N 3.70; found: C 50.98, H 7.31, N 3.96.
7.0Hz, 3H), 1.20 1.61 (m, 6H), 1.45 (s, 9H), 1.48 (s, 9H), 1.56 (s, 9H),
1.98 2.07 (m, 1H), 2.16 2.27 (m, 2H), 2.32 2.44 (m, 1H), 4.64 (d, J ˆ
0.8 Hz, 1H), 4.67 4.82 (m, 2H), 4.68 (d, J ˆ 0.8 Hz, 1H); 13C NMR
(75 MHz, C6D6): d ˆ 16.43, 16.54, 20.95, 21.17, 22.01, 22.13, 23.38, 23.50,
26.26, 26.66, 30.54, 31.37, 31.44, 31.77, 32.11, 34.37, 34.45, 40.75, 40.81, 47.34,
47.43, 63.96, 64.34, 69.29, 74.80, 75.48, 82.09, 83.31, 172.81, 172.94; IR (KBr):
nÄ ˆ 2937, 2902, 2344, 2335, 1740, 1348, 1160, 911, 705 cmÀ1; MS (EI): m/z
Asymmetric diamination of bis[(À)-menthyl] fumarate (50) with osmium
complex 3: Bis[(À)-menthyl] fumarate (295 mg, 0.75 mmol) was added to a
solution of tris(N-tert-butylimido)oxoosmium(viii) (3) (210mg, 0.5 mmol)
in freshly distilled THF (5 mL). The resulting brown solution was stirred at
RT for 5 h during which it turned dark red. The solvent was removed under
reduced pressure to leave a red-brown oil which was analysed by 1H NMR
and the purified by column chromatography on silica gel (hexanes/ethyl
acetate 4:1). After evaporation of the solvents under reduced pressure, the
pure mixture of the two diastereomers (378 mg, 0.47 mmol, 93% yield) was
separated by semipreparative HPLC (Knauer Eurospher 100 CN,
tBuOCH3/n-hexane 20:80, 14 mLmin À1, 366 nm); tR ˆ 10.6 min for 55 and
11.7 min for 54; analytical HPLC: Knauer Eurospher 100 CN, 254 nm,
n-hexane/tBuOCH3 80:20, 1.0 mLmin À1; tR ˆ 9.7 min [(À)-54], 8.1 min
[(‡)-53].
‡
(%): 813 (4) [M] , 575 (100), 437 (17), 393 (22), 337 (15), 281 (16);
elemental analysis calcd (%) for C36H67N3O5Os: C 53.24, H 8.32, N 5.17;
found: C 53.37, H 8.22, N 5.55.
Attempted enantioselective diamination in the presence of cinchona
alkaloid ligands: A representative experiment was performed as follows: A
solution of the appropriate chiral cinchona alkaloid ligand (1.2 mmol) and
the osmium reagent 2 (364 mg, 1 mmol) in THF (5 mL) was stirred at RT
under Ar. The respective olefin (2 mmol) was added in one portion at RT
against a positive stream of Ar and the resulting reaction mixture was
stirred at RT overnight. Standard work-up and column chromatography
gave the corresponding osmaimidazolidine that was purified by column
chromatography as described above for the individual compound and
analysed by chiral HPLC.
(4R,5R)-trans-1,3-Bis(tert-butyl)-2-oxo-2-tert-butylimido-4,5-bis[(À)-men-
thyloxycarbonyl]-2-osma(vi)imidazolidine (53): Obtained as an orange to
brown solid; [a]2D8 ˆ ‡595 (c ˆ 0.15); 1H NMR (300 MHz, C6D6): d ˆ 0.56
1.11 (m, 8H), 0.74 (d, J ˆ 6.2 Hz, 3H), 0.77 (d, J ˆ 6.4 Hz, 3H), 0.79 (d, J ˆ
7.2 Hz, 3H), 0.82 (d, J ˆ 7.0Hz, 3H), 0.87 (d, J ˆ 7.0Hz, 3H), 0.97 (d, J ˆ
7.0Hz, 3H), 1.22 1.65 (m, 8H), 1.46 (s, 9H), 1.47 (s, 9H), 1.57 (s, 9H),
1.94 2.16 (m, 3H), 2.26 2.32 (m, 1H), 4.65 (d, J ˆ 0.6 Hz, 1H), 4.76 (dt,
J ˆ 4.3, 10.3 Hz, 1H), 4.90 (d, J ˆ 0.6 Hz, 1H),4.95 (dt, J ˆ 4.4, 10.4 Hz);
13C NMR (75 MHz, C6D6): d ˆ 14.27, 16.26, 16.34, 20.69, 21.05, 22.07, 22.13,
23.32, 23.59, 26.07, 26.69, 30.49, 31.35, 31.52, 31.85, 32.8, 34.21, 34.26, 41.00,
41.10, 46.95, 63.50, 64.09, 74.91, 75.61, 80.83, 82.04, 172.84, 173.16; IR
(KBr): nÄ ˆ 2944, 2919, 2341, 2327, 1747, 1354, 1165, 907, 702 cmÀ1; MS (EI):
Osmaimidazolidine 11: Daicel Chiralpak AS, 254 nm, n-hexane/2-propanol
98:2, 0.5 mLminÀ1; tR ˆ 13.5 min [(‡)-11], 15.6 min [(À)-11].
Osmaimidazolidine 36: Daicel Chiralpak AS, 254 nm, n-hexane/2-propanol
98:2, 0.5 mLminÀ1; tR ˆ 13.5 min [(‡)-36], 15.6 min [(À)-36]. No full
baseline separation was achieved.
trans-1,3-Bis(tert-butyl)-2,2-dioxo-4,5-bis(ethyloxycarbonyl)-2-osma(vi)-
imidazolidine (59):[21] Obtained from a diamination as described above
(88% chemical yield on a 1 mmol scale) as racemic material. 1H NMR
(300 MHz, C6D6): d ˆ 0.96 (t, J ˆ 7.2 Hz, 6H), 1.19 (s, 18H), 3.87 (q, J ˆ
7.2 Hz, 4H), 4.54 (s, 2H); 13C NMR (75 MHz, C6D6): d ˆ 12.68, 28.62, 60.32,
65.33, 79.41, 170.53; IR (KBr): nÄ ˆ 2974, 1738, 1367, 1288, 1230, 1186, 1028,
‡
m/z (%): 813 (3) [M] , 575 (100), 437 (21), 393 (30), 337 (16), 281 (11);
elemental analysis calcd (%) for C36H67N3O5Os: C 53.24, H 8.32, N 5.17;
found: C 53.03, H 8.49, N 5.42.
(4S,5S)-trans-1,3-Bis(tert-butyl)-2-oxo-2-tert-butylimido-4,5-bis[(À)-men-
thyloxycarbonyl]-2-osma(vi)imidazolidine (54): Obtained as a brownish
solid; [a]2D8 ˆ À976 (c ˆ 0.02); 1H NMR (300 MHz, C6D6): d ˆ 0.69 1.11
(m, 10H), 0.72 (d, J ˆ 6.4 Hz, 3H), 0.79 (d, J ˆ 6.4 Hz, 3H), 0.86 (d, J ˆ
7.0Hz, 3H), 0.87 (d, J ˆ 7.0Hz, 3H), 0.93 (d, J ˆ 7.0Hz, 3H), 0.97 (d, J ˆ
‡
904, 895 cmÀ1; MS (EI): m/z (%): 538 (5) [M] , 465 (47), 409 (19), 353 (23),
57 (100); HRMS: calcd for C16H30N2O6188Os: 534.1661, found: 534.1656;
analytical HPLC: Daicel Chiralpak AS, 254 nm, n-hexane/2-propanol 98:2,
0.5 mLminÀ1, tR ˆ 18.7 min [(‡)-59], 24.4 min [(À)-59].
Table 5. Crystallographic data, structure solution and refinement of 12, 13, 28, 32 and 53.
12
13
28
32
53
formula
Mr
dimensions [mm]
crystal system
space group
a [ä]
b [ä]
c [ä]
a [8]
b [8]
C18H28N2O4Os
526.62
0.25 Â 0.10 Â 0.05
orthorhombic
Pbca (no.61)
13.6907(2)
C21H34N2O4Os
568.70567.72
0.50 Â 0.25 Â 0.10
monoclinic
P21/c (no.14)
11.4893(3)
C21H35N3O3Os
572.69
C23H30N2O3Os
812.13
0.40 Â 0.20 Â 0.10
monoclinic
P21)/c (no.14)
17.6484(4)
C36H67N3O5Os
0.30 Â 0.20 Â 0.10
0.30 Â 0.05 Â 0.05
monoclinic
P21 (no.4)
9.2730(1)
40.2510(6)
10.4253(2)
triclinic
≈
P1 (no.2)
10.3714(2)
10.7095(3)
10.9049(3)
94.173(1)
108.464(1)
92.358(1)
1143.20(5)
2
1.649
5.602
564
123(2)
15.2685(2)
18.8178(2)
14.6163(4)
14.2195(4)
8.4448(2)
15.3884(3)
105.631(1)
100.608(1)
94.291(1)
g [8]
V [ä3]
Z
3933.61(9)
8
1.778
6.507
2064
2299.58(11)
4
1.643
5.572
1128
2254.25(9)
4
1.687
5.682
1128
3880.31(10)
4
1.390
3.327
1680
1 [gcmÀ3
]
]
m [mmÀ1
F(000)
T [K]
123(2)
50.0
123(2)
50.0
123(2)
50.0
123(2)
50.0
2qmax [8]
50.0
À 16 ꢀ h ꢀ 16
À 18 ꢀ k ꢀ 18
À 22 ꢀ l ꢀ 22
30158
À 13 ꢀ h ꢀ 13
À 17 ꢀ k ꢀ 17
À 16 ꢀ l ꢀ 16
23304
À 12 ꢀ h ꢀ 12
À 12 ꢀ k ꢀ 12
À 12 ꢀ l ꢀ 12
20431
À 20 ꢀ h ꢀ 20
À 9 ꢀ k ꢀ 10
À 18 ꢀ l ꢀ 18
19923
À 11 ꢀ h ꢀ 11
À 47 ꢀ k ꢀ 47
À 12 ꢀ l ꢀ 12
25325
no. measured data
no. unique data
3459
4050
4013
3955
13097
Rint
0.0702
F2
0.0701
F2
0.0798
F2
0.0712
F2
0.0924
F2
refinement on
no. parameters/restraints
R[for I > 2s(I)]
226/0253/0251/67
0.0193
262/0371/1
0.0315
0.0239
0.0328
0.0497
wR2 (all data)
max./min. difference peak [eäÀ3
0.0428
À 0.618/0.905
0.0776
À 2.651/2.213
0.0601
À 1.356/1.051
0.0883
À 2.600/2.437
0.0941
À 1.749/1.573
]
5594
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2003, 9, 5581 5596

Diamination of Olefins
5581 5596
Crystal structure determination of osmaimidazolidine complexes 12, 13, 28,
32 and 53: The data were collected on a Nonius KappaCCD diffractometer
at À1508C with MoKa radiation (l ˆ 0.71073 ä). The structures of 28 and
53 were solved by direct methods and those of 12, 13 and 32 were solved by
Patterson methods (SHELXS-97[71]). The non-hydrogen atoms were
refined anisotropically, H atoms were refined by using a riding model
(full-matrix least-square refinement on F2(SHELXS-97[72]). Details of data
collection and refinement are given in Table 5. Empirical absorption
collections from multiple reflections were applied for all 12, 13, 28, 32 and
53. The absolute configuration of 53 was determined by using the Flack
parameter [x ˆ À0.07(1)].[73] Due to the low quality of the crystals ib 54
only the Os atoms were refined anisotropically.
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¬
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CCDC-206066 (12), -206067 (13), -206068 (28), -206069 (32) and -206070
(53) contain the supplementary crystallographic data for this paper. These
data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/
retrieving.html (or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB21EZ, UK; (fax: (‡44)1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk).
¬
[12] Selected examples: a) Z. Li, M. Fernandez, E. N. Jacobsen, Org. Lett.
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Acknowledgement
K.M. is most grateful to Prof. Dr. J. Barluenga and his colleagues at the
University of Oviedo for discussions and continuous encouragement over
recent years. K.M. acknowledges Prof. Dr. K. H. Dˆtz for his support at the
¬
Kekule-Department at Bonn and the Fonds der Chemischen Industrie for a
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Liebig-Stipend 2000/2003. The authors are grateful to Mr. H. C. Jahr for
assistance in preparing some of the graphical material and to Mr. A.
Schneider for HPLC analyses.
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Chem. Eur. J. 2003, 9, 5581 5596
www.chemeurj.org
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5595

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K. Muniz et al.
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À
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[44] The products obtained thereby are interesting derivatives of a,b-
diamino acids that represent biologically interesting compounds. See,
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[45] For original work by Sharpless on reaction of 1 with olefins, see:
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Received: April 1, 2003 [F5011]
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