Orientation in the metalation of amide, carbamate, ureido, and allylic derivatives of cymantrene

Article abstract of DOI:10.1007/s11172-012-0327-8

The orientation in the metalation of monosubstituted carbamate-, amide-, ureido-, and allyl-containing derivatives of cymantrene was determined for the first time. The data obtained open up a synthetic route to polyfunctional 1,2- and 1,3-disubstituted cymantrenes. They can serve as the starting materials for the preparation of chelate complexes of (dicarbonyl)-(cyclopentadienyl) manganese, which hold promise as novel organometallic photochromes. A method for the synthesis of earlier unknown chiral derivatives of cymantrene with a quaternary carbon atom in position 1 of the side chain was proposed.

Full text of DOI:10.1007/s11172-012-0327-8

Russian Chemical Bulletin, International Edition, Vol. 61, No. 12, pp. 2326—2337, December, 2012
2326
Orientation in the metalation of amide, carbamate, ureido,
and allylic derivatives of cymantrene
E. S. Kelbysheva, L. N. Telegina, I. A. Godovikov, T. V. Strelkova, A. F. Smol´yakov, F. M. Dolgushin, and N. M. Loim
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: loim@ineos.ac.ru
The orientation in the metalation of monosubstituted carbamateꢀ, amideꢀ, ureidoꢀ, and
allylꢀcontaining derivatives of cymantrene was determined for the first time. The data obtained
open up a synthetic route to polyfunctional 1,2ꢀ and 1,3ꢀdisubstituted cymantrenes. They can
serve as the starting materials for the preparation of chelate complexes of (dicarbonyl)ꢀ
(cyclopentadienyl)manganese, which hold promise as novel organometallic photochromes.
A method for the synthesis of earlier unknown chiral derivatives of cymantrene with a quaterꢀ
nary carbon atom in position 1 of the side chain was proposed.
Key words: cymantrene, metalation, regioselectivity, polyfunctional 1,2ꢀ and 1,3ꢀdisubꢀ
stituted cymantrenes, Xꢀray diffraction study.
Metalation of monosubstituted derivatives of (cycloꢀ
pentadienyl)(tricarbonyl)manganese (also referred to as
cymantrene) with butyllithium followed by a reaction of
the metalation product with an electrophilic reagent unꢀ
derlies a straightforward and efficient route to disubstitutꢀ
ed cymantrene derivatives.1,2 Metalation of monosubstiꢀ
tuted cymantrene derivatives such as hydroxymethylꢀ
cymantrene,3,4 cyclic acetals of cymantrenecarbaldehyde,5
1ꢀ(dimethylamino)alkylcymantrene,6,7 dimethylsulfaꢀ
moylcymantrene,8 2ꢀcymantrenyloxazolidines,9 and 2ꢀcyꢀ
mantrenyloxazolines10,11 results in preferential or selecꢀ
tive formation of chiral 1,2ꢀdisubstituted cymantrene deꢀ
rivatives. Lithiation of the enantiomers of 1ꢀ(dimethylꢀ
amino)ethylcymantrene,12 2ꢀcymantrenyloxazolines,11
(R,R)ꢀ2ꢀcymantrenylꢀ3ꢀphenylꢀ1,3ꢀdioxalane,5 and
(2S,4S,5R)ꢀ2ꢀcymantrenylꢀ3,4ꢀdimethylꢀ5ꢀphenylꢀ1,3ꢀ
oxazolidine9 proceeds stereoselectively to give optically
active 1,2ꢀdisubstituted cymantrene derivatives. The only
example of regioselective metalation of cymantrene derivꢀ
atives that affords 1,3ꢀdisubstituted derivatives is a reacꢀ
tion of diphenylphosphinocymantrene with butyllithium.3
In the present work, we studied for the first time the
regioꢀ and stereoselectivity of metalation of monosubstiꢀ
tuted cymantrene derivatives containing the carbamate,
amide, ureido, or allyl group in the substituent. These
compounds were used because we search for approaches
to the synthesis of polyfunctional disubstituted cymanꢀ
trene derivatives with photochromic properties.13—15
Earlier,16 it has been demonstrated that metalation
of carbamates of primary benzylamines with ButLi
(2—3 equiv.) gives orthoꢀsubstituted products in ~50%
yield. We found that a reaction of cymantrenyl carbamꢀ
ate 1 with 2.8 equiv. of BunLi in THF at –65 C for 1 h
followed by quenching with D2O allows regioselective inꢀ
troduction of deuterium into diastereotopic positions 2
and 5 of the Cp ring (Scheme 1). Analysis of the integral
intensity ratio of the signals for the protons in positions 2
1
and 5 of the Cp ring at  5.13 and 5.17 in the H NMR
spectra shows that the ratio of the diastereomers of deuꢀ
terated carbamate derivative 1ꢀD is 1 : 2. Treatment of
a mixture of lithiated derivatives of carbamate 1 with diꢀ
methylformamide gives a mixture of two aldehydes 2a,b
with the same ratio of diastereomers (60% conversion;
a 63% yield with respect to the consumed carbamate) (see
Scheme 1
Boc = OCOBut
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2304—2315, December, 2012.
1066ꢀ5285/12/6112ꢀ2326 © 2012 Springer Science+Business Media, Inc.

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
2327
Scheme 1). An increase in the metalation time of comꢀ
pound 1 to 2 h results in no appreciable increase in its
conversion, while conduction of the reaction at –40 lowꢀ
ers the yield of compounds 2a,b to 20—30%.
noted when a lithium salt of (R)ꢀ3 is treated with ethyl
iodide or benzyl bromide. However, partial racemization
occurs in this case: the optical purity of compounds 4 and
5 was 61 and 12%, respectively. This reaction pathway of
metalation of secondary carbamates opens up a route to
novel chiral cymantrene derivatives containing a quaterꢀ
nary carbon atom in position 1 of the side chain. For
instance, a reaction of a lithium salt of compound 3
with benzaldehyde yields oxazolidine 6 (see Scheme 2).
The 1H NMR spectrum of this compound shows only one
set of signals, which suggests a stereoselective character
of the reaction leading to only one of two possible diaꢀ
stereomers.
It should be noted that metalation of related carbamꢀ
ates of primary 1ꢀferrocenylalkylamines with excess BunLi
allows introduction of lithium into the unsubstituted Cp
ring and exclusive formation, upon the addition of an elecꢀ
trophile, of 1,1´ꢀdisubstituted ferrocene derivatives in high
yields.17 Therefore, the low yields of lithiation products
obtained from carbamates of primary cymantrenylalkylꢀ
and cymantrenylbenzylamines can be attributed to a long
distance between carbamateꢀcoordinated BuLi and the
aromatic ring.
Protophilic substitution involving butyllithium is known
for its very high kinetic isotopic effect.6,20,21 As a result,
metalation of deuterated analogs follows a substitution
pathway that differs from that when nondeuterated comꢀ
pounds are used. Indeed, treatment of monodeuterated
carbamate 3ꢀD with butyllithium followed by addition of
D2O to the reaction system gave dideuterated carbamate
3ꢀD2 containing deuterium atoms in both the side chain
and the Cp ring (see Scheme 2). The ring deuterium atom
is distributed between three positions of the Cp ring with
a  :  : ´ ratio of 1 : 3 : 1. This pathway of the metalation
reaction is obviously due to the presence of a bulky sideꢀ
chain substituent that prevents introduction of lithium into
the ꢀposition of the Cp ring, which luckily provides the
rare possibility of controlling the stereoselective substituꢀ
tion into the ꢀposition of the Cp ring. The relatively high
regioꢀ and stereoselectivities of the metalation of comꢀ
pound 3ꢀD open up a new synthetic route to optically
active 1,3ꢀdisubstituted cymantrene derivatives.
Metalation of Nꢀ(tertꢀbutoxycarbonyl)ꢀNꢀmethylꢀ1ꢀ
cymantrenylethylamine (3) with BunLi (2.8 equiv.) folꢀ
lowed by quenching with D2O unexpectedly yielded its
deuterated analog 3ꢀD containing the deuterium atom in
position 1 of the substituent rather than in the Cp ring
(Scheme 2), which has never been observed before in the
metalation of cymantrene derivatives. This reaction outꢀ
come suggests that either the acidity of the CH group in
the fragment CHNMeBoc is higher than the CHꢀacidity
of the Cp ligand of cymantrene or the carbamateꢀcoordiꢀ
nated BuLi attacks the nearest C—H bond because of steric
hindrances. A similar direction of lithiation has been obꢀ
served for Bocꢀsubstituted secondary benzylamines.18,19
Metalation of the (R)ꢀenantiomer of carbamate 3 folꢀ
lowed by quenching with D2O gave its deuterated analog
3ꢀD, which has the same configuration of the chiral center
and retains high optical purity (ee > 99%). The retention
of the configuration of the chiral center has been also
Scheme 2
R = Et (4), Bn (5)

2328
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
Kelbysheva et al.
Earlier,17 it has been shown that metalation of
1ꢀ(pivaloylamino)ethylferrocene with butyllithium gives
1,2ꢀdisubstituted ferrocene derivatives with de = 87%. In
contrast, a reaction of cymantrenyl amide 7 with BunLi
(2.8 equiv.) followed by quenching with D2O allows regioseꢀ
lective but not stereoselective introduction of the deuteriꢀ
um atom into the ꢀposition of the Cp ring; the yield of
product 7ꢀꢀD is 50% (Scheme 3). In the case of amides 8
and 9, deuterium does not enter into the ring: the starting
and final compounds are identical. When the reaction time
was extended or TMEDA was used, the deuterium conꢀ
tent in the Cp ring of all three amides 7—9 did not inꢀ
crease. Thus, a bulkier substituent at the C=O group preꢀ
vents an interaction of the amideꢀcoordinated BunLi with
the C—H bonds of the Cp ring. In contrast, protophilic
substitution in secondary amide 10 results in regioselecꢀ
tive introduction of deuterium into the ꢀposition of the
Cp ring, and the yield of product 10ꢀꢀD is 85%. No
lithiation occurs at the sideꢀchain Cꢀ1 atom even when
two equivalents of BunLi are used, in contrast to carbamꢀ
ate 2 (see Scheme 3).
Table 1. Yields (%) and the deuterium content of the Cp ring in
the metalation products obtained from amides 11—13 (calculatꢀ
ed from the MS data by the Ariadna program24
)
Starting
Metalation products
compound
11ꢀD—13ꢀD
14
15
16a—c 17a—c
11
16%
0.64 Da
82%
8%
5%
0.37 D
2%
0.15 D
8%
0.26 D
6%
0.17 D
3%
64%
3%
5%
0.06 D
8%
0.08 D
18%
0.06 D
7%
0.06
12b
12c
13b
13c
2%
9%
0.73 Da
47%
13%
4%
0.72 Da
42%
39%
17%
0.74 Da
76%
3%
0.08 D
0.67 Da
0.22 D
a The ratio of the ꢀ and ꢀsubstitution products is  9 : 1.
b The direct order of addition of the reagents.
c The reverse order of addition of the reagents.
nonequivalent protons in the 1H NMR spectra of diaꢀ
stereomeric alcohols 17a—c suggest stereoselective addiꢀ
tion of BunLi to the prochiral carbonyl group of keꢀ
tones 16a—c.
Scheme 3
It can be seen in Table 1 that the ratio of the products
depends on both the nature of the substituents at the
N atom and the order of addition of the reagents to the
reaction system. For instance, metalation of amide 11
gives keto amide 17a as the major product (64%), while
amides 12 and 13 are mainly converted into their deuterꢀ
ated analogs 12ꢀD and 13ꢀD (82 and 76%, respectively)
(see Table 1).
Compound
7
8
9
R
H
H
H
Me
R´
Me
Ph
O(4)
But
Me
10
C(23)
C(9)
Mn(1)
C(7)
C(4)
N(1)
Metalation of tertiary amides of benzoic22 and ferꢀ
rocenecarboxylic23 acids ensures selective synthesis of the
corresponding 1,2ꢀdisubstituted derivatives. Reactions
of BunLi with cymantrenecarboxamides 11—13 followed
by quenching of the lithiation products with D2O
also result in regioselective introduction of deuterium
into the ꢀposition of the Cp ring (Table 1). Howꢀ
ever, along with deuterated analogs of the starting amides
(11ꢀD—13ꢀD), the reactions yielded butyl cymantreꢀ
nyl ketone (14), dibutyl cymantrenyl carbinol (15), keto
amides 16a—c, and hydroxy amides 17a—c (Scheme 4).
These products were isolated by column chromatography
and identified using mass spectrometry and elemenꢀ
tal analysis. The molecular structure of the diaꢀ
stereomer 1ꢀcymantrenylꢀ1ꢀ[2ꢀ(N,Nꢀdiethylcarbamoyl)ꢀ
cymantrenyl]pentanol (17b) was determined by Xꢀray
diffraction (Fig. 1, Table 2). Xꢀray diffraction data as
well as the presence of the unique sets of signals for all
C(5)
C(8)
O(3)
C(3)
C(25)
C(24)
C(26)
C(22)
O(8)
C(6)
C(2)
O(2)
H(10)
C(14)
C(10)
C(13)
C(12)
O(1)
C(19)
C(1)
C(11)
C(18)
C(20)
Mn(2)
C(17)
C(16)
C(21)
O(7)
C(15)
O(6)
O(5)
Fig. 1. Structure of complex 17b´ with atomic numbering (the
H atoms, except for those of the hydroxyl group, are omitted).

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
2329
Scheme 4
11: R = R´ = Me; 12: R = R´ = Et; 13: R = Me; R´ = Ph; 16: R = R´ = Me (a); R = R´ = Et (b); R = Me; R´ = Ph (c)
17: R = R´ = Me (a); R = R´ = Et (b); R = Me; R = Ph (c)
Replacement of the direct order of mixing the reagents
(when BunLi is added to a solution of the amide) by the
reverse order (when the amide is added to a solution of
BunLi) produces opposite results for amides 12 and 13.
For this reason, to increase the yield of some or other
metalation product of cymantrenecarboxamides, one
should individually select the order of addition of the
reagents.
It is seen from Table 1 that the metalation of amides
11—13 is highly regiospecific with respect to the ꢀposiꢀ
tion of the Cp ring: the ratio of the ꢀ and ꢀsubstitution
products in compounds 11ꢀD—13ꢀD is 9 : 1. In addition,
deuterium is also present in the Cp rings of alcohols 15
and 17a—c (6—37% D) formed as byꢀproducts. Thereꢀ
fore, these compounds are formed prior to the addition of
D2O to the reaction mixture.
To locate the deuterium atom in the Cp ring, the deuꢀ
terated analogs of amides 11—13 were isolated and reꢀ
duced to the corresponding amines 18a—c (Scheme 5).
The signals for the protons of the Cp ring in the 1H NMR
spectra of these compounds were assigned by comparing
them with the spectra of the corresponding ꢀdeuterated
amines obtained independently from ꢀdeuterated cymanꢀ
trenylmethanol (19)3,4 (see Scheme 5).
Whereas metalation of Nꢀbenzylurea fails to introduce
lithium into the aromatic ring,25 reactions of BunLi
(2 equiv.) with N,NꢀdialkylꢀN´ꢀferrocenylmethylureas
mainly give heteroannular ferrocene derivatives.17 In the
Table 2. Selected bond lengths (d) in structures 17b´ and 17b
Bond
d/Å
Bond
d/Å


17b
17b´
17b
17b´
Mn(1)—C(2)
Mn(1)—C(3)
Mn(1)—C(4)
Mn(1)—C(5)
Mn(1)—C(6)
Mn(2)—C(10)
Mn(2)—C(11)
Mn(2)—C(12)
Mn(2)—C(13)
Mn(2)ꢀC(14)
O(1)—C(1)
2.166(3)
2.148(3)
2.137(3)
2.152(3)
2.163(3)
2.181(3)
2.163(3)
2.138(3)
2.129(3)
2.147(3)
1.419(3)
0.79(3)
2.156(3)
2.160(3)
2.145(3)
2.155(3)
2.155(3)
2.167(3)
2.148(3)
2.131(3)
2.118(3)
2.140(3)
1.420(3)
0.72(3)
N(1)—C(25)
C(1)—C(2)
C(1)—C(10)
C(1)—C(18)
C(2)—C(3)
1.469(3)
1.536(3)
1.536(3)
1.538(3)
1.456(3)
1.417(3)
1.430(3)
1.499(3)
1.412(3)
1.428(3)
1.416(3)
1.438(3)
1.428(3)
1.421(3)
1.419(3)
1.477(4)
1.530(4)
1.532(4)
1.531(4)
1.441(4)
1.426(4)
1.427(4)
1.500(4)
1.407(4)
1.414(4)
1.423(4)
1.435(4)
1.426(5)
1.406(5)
1.418(4)
C(2)—C(6)
C(3)—C(4)
C(3)—C(22)
C(4)—C(5)
C(5)—C(6)
C(10)—C(11)
C(10)—C(14)
C(11)—C(12)
C(12)—C(13)
C(13)—C(14)
O(1)—H(1O)
O(8)—C(22)
N(1)—C(22)
N(1)—C(23)
1.245(3)
1.352(3)
1.483(3)
1.240(3)
1.347(4)
1.483(4)

2330
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
Kelbysheva et al.
Scheme 5
Scheme 7
cymantrenecarbaldehyde (26) in 24% yield (Scheme 8).
The structure of compound 26 was determined from
HHꢀCOSY and HHꢀROESY NMR data. The HHꢀCOSY
spectrum (Fig. 2, a) shows crossꢀpeaks between the sigꢀ
nals for the protons of the Cp ring at  5.70 and 5.61 but
does not reveal a spinꢀspin coupling with the proton manꢀ
ifested by a highꢀfield signal at  5.16. The HHꢀROESY
spectrum (Fig. 2, b) shows dipolar couplings of the proton
of the aldehyde group ( 9.65) only with the protons of the
Cp ring that resonate at  5.70 and 5.61. This direction of
metalation is obviously due to the presence of the bulky
substituent, which precludes lithiation at the ꢀposition of
the Cp ring.
case of cymantrenylꢀcontaining urea 21, treatment of
a lithium derivative with allyl bromide allows regioselecꢀ
tive synthesis of 1,2ꢀdiastereomers 22 in a ratio of 1 : 1.3
(HHꢀCOSY and HHꢀROESY NMR data) (Scheme 6).
Thus, the ureido group acts as an efficient ꢀdirector in
the lithiation.
Scheme 6
Scheme 8
A reaction of lithiated derivatives of allyloxymethylꢀ
cymantrene 27 with dimethylformamide yielded 1,2ꢀ and
1,3ꢀdisubstituted products 28 and 29 in a ratio of 2 : 1, for
which the  values of the formyl protons are 9.66 and 9.84,
respectively (Scheme 9). The structures of these isoꢀ
mers were determined using 2D NMR experiments. The
HHꢀCOSY spectrum of the major isomer 28 reveals
a correlation between all three protons of the disubstitutꢀ
ed Cp ring with the signals at  5.68, 5.26, and 5.12. The
HHꢀROESY spectrum shows crossꢀpeaks between the sigꢀ
nals for the formyl group ( 9.84), the CH2 protons of the
allyl group ( 4.55), and the proton of the Cp ring ( 5.26).
The HHꢀCOSY and HHꢀROESY patterns of the minor
isomer 29 are similar to that given above for aldehyde 26
(see Fig. 2). Therefore, isomers 28 and 29 can be assigned
to 1,2ꢀ and 1,3ꢀderivatives of cymantrene, respectively.
Apparently, preferential ꢀmetalation of compound 27 is
As with amide 3, metalation of N,N´ꢀdimethylꢀN´ꢀ
phenylurea (23) occurs at the sideꢀchain Cꢀ1 atom and
a subsequent reaction with allyl bromide gives cymantrene
derivative 24 containing a quaternary chiral carbon center
in position 1 of the side chain in 55% yield (Scheme 7).
The cymantrene derivatives discussed above contain
the fragment NC=O in the substituent, which ensures prefꢀ
erential ꢀmetalation of the Cp ring. In contrast, a reacꢀ
tion of allylcymantrene 25 with BunLi followed by treatꢀ
ment of lithiation products with dimethylformamide
allows regioꢀ and stereoselective synthesis of 3ꢀallylꢀ

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
a
2331
b
, ppm
, ppm
1
2
3
4
5
6
2
4
6
8
6
5
4
3
2
1
, ppm
8
6
4
2 , ppm
Fig. 2. HHꢀCOSY (a) and HHꢀROESY spectra (b) of a solution of compound 26 in acetoneꢀd6.
due to the presence of the oxygen atom in the substituent
which coordinates the lithium atom of BunLi and directs
its attack on the proximate position of the Cp ring.
planar chiral disubstituted cymantrenyl fragment) are
identical (Table 3). The dihedral angle between the planes
of the Cp rings of the cymantrenyl fragments in structures
17b´ and 17b is 90.6 and 75.8, respectively. Both strucꢀ
tures are stabilized by the strong intramolecular hydrogen
bonds O(1)—H(1O)...O(8) (O(1)...O(8), 2.703(5) (17b´)
and 2.699(3) Å (17b)). These bonds persist in solution as
well, which is evident from the presence of a signal for the
Scheme 9
1
proton of the hydroxyl group at  6.75 in the H NMR
spectrum of compound 17b. A lowꢀfield signal for the hyꢀ
droxyl proton also appears in the spectra of alcohols 17a,c.
C(4)
C(5)
N(1)
Mn(1)
C(22)
C(3)
Compound 17b forms yellow crystals of two types
(prisms (17b´) and plates (17bІ)) in the same space group
P21/c but with different unit cell parameters (see Table 3).
The principal difference between the complexes in the
crystals of 17b´ and 17b arises from different orientations
of the ethyl groups in the amide substituent (Fig. 3).
In structure 17b´, both ethyl groups are oriented in the
same direction relative to the plane of the amide substituꢀ
ent (the torsion angle C(24)—C(23)—C(25)—C(26) is
30.4), while in structure 17b, these groups are oriented
in opposite directions relative to the plane of the amide subꢀ
stituent (the torsion angle C(24)—C(23)—C(25)—C(26)
is 138.2). Otherwise, structures 17b´ and 17b show no
fundamental differences; the relative configurations of the
chiral centers (the C(1) atom and the C(3) atom of the
C(6)
O(8)
C(2)
C(1)
O(1)
Mn(2)
Fig. 3. Superposition of the molecules in structures 17b´ (dashed
line) and 17b (solid line).

2332
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
Kelbysheva et al.
isomer. 1H NMR (acetoneꢀd6), : 1.44 (d, 3 H, CHMe, J = 9.0 Hz);
1.46 (s, 9 H, CMe3); 3.83 (m, 1 H, CHMe); 4.92 (br.d, 1 H, NH,
J = 12.0 Hz); 5.03 (m, 1 H, HCp); 5.14 (m, 1 H, HCp); 5.42
(m, 1 H, HCp); 5.74 (m, 1 H, HCp); 9.94 (s, 1 H, CHO). Minor
isomer. 1H NMR (acetoneꢀd6), : 1.33 (d, 3 H, CHMe, J = 9.0 Hz);
1.41 (s, 9 H, CMe3); 3.25 (m, 1 H, CHMe); 3.83 (m, 2 H, HCp);
5.14 (m, 1 H, HCp); 5.51 (m, 1 H, HCp); 5.78 (br.s, 1 H, NH);
9.83 (s, 1 H, CHO). Found (%): C, 51.12; H, 4.93; N, 3.82;
Mn, 14.5. C16H18MnNO6. Calculated (%): C, 51.21; H, 4.88;
N, 3.73; Mn, 14.64.
To sum up, we were the first to determine the orientaꢀ
tion in the metalation of monosubstituted carbamateꢀ,
amideꢀ, ureidoꢀ, and allylꢀcontaining derivatives of cyꢀ
mantrene. The results obtained open up a synthetic route
to polyfunctional 1,2ꢀ and 1,3ꢀdisubstituted cymantrenes,
which can serve as the starting materials for the preparaꢀ
tion of chelate complexes of (dicarbonyl)(cyclopentaꢀ
dienyl)manganese that hold promise as novel organoꢀ
metallic photochromes.
(R)ꢀNꢀtertꢀButoxycarbonylꢀNꢀmethylꢀ1ꢀcymantrenylethylꢀ
amine ((R)ꢀ3) was obtained from (R)ꢀ1 (1.6 g, 4.6 mmol) as
described for the synthesis of compound 3. Yield 1.3 g (71%),
yellow oil. The product is a 3 : 2 mixture of two conformers.
Experimental
1
H and 13C NMR spectra were recorded on a Bruker Avance
1
Major conformer. H NMR (benzeneꢀd6), : 1.01 (d, 3 H, Me,
400 spectrometer (400.13 and 100.61 MHz, respectively) with
Me4Si as the internal standard. The signals in the 1H NMR
spectra were assigned using 2D experiments (COSY and ROESY)
or selective deuteration. IR spectra were recorded on a Magna
750ꢀIR FTIR spectrometer (Nicolet) (resolution 2 cm–1) in KBr
pellets. Mass spectra (EI, 70 eV) were measured on Kratos MS
890 and Finnigan POLARIS Q spectrometers. The course of the
reactions was monitored and the purity of the products was
checked by TLC on Silufol UVꢀ245 plates (Kavalier). Silica gel
60 (Merck) was used for column chromatography. Enantiomeric
analysis was carried out by HPLC (Daicel Chiralcel ODꢀH) and
GLC (ꢀdextrin as a stationary phase). The solvents used (THF,
hexane, and benzene) were purified routinely and distilled over
sodium or sodium benzophenone ketyl in an atmosphere of arꢀ
gon. The syntheses of carbamates 1, (R)ꢀ1, and 3 and their
ꢀdeuterated analogs have been already documented.14 Allylꢀ
oxymethylcymantrene 27 was prepared as described earlier.15
Metalation of cymantrene derivatives followed by treatment
with an electrophile (general procedure I). A required amount of
BunLi (as a 1.6 M solution in hexane) was added dropwise at
–70 C for 0.5—2 h to a stirred 0.1 M solution of a substrate to be
metalated in anhydrous THF. The reaction mixture was stirred
at the same temperature for 1—2 h and treated with an appropriꢀ
ate electrophile (D2O, DMF, allyl bromide, ethyl bromide,
benzyl bromide, or benzaldehyde). Then the reaction mixture
was warmed to room temperature for 1 h and neutralized with
20% H3PO4 or 10% NH4Cl. The product was extracted with
diethyl ether. The extracts were washed with water, dried over
Na2SO4, and concentrated. The residue was purified by column
chromatography on silica gel with hexane—ethyl acetate (3 : 1)
as an eluent.
NꢀtertꢀButoxycarbonylꢀ1ꢀ(2ꢀdeuterocymantrenyl)ethylamine
(1ꢀD) was obtained according to general procedure I from comꢀ
pound 1 (1.6 g, 4.6 mmol), BunLi (8 mL, 12.8 mmol), and D2O
(1 mL, 50 mmol). The residue was recrystallized from hexane.
Yield 1.4 g (87.5%), m.p. 77—79 C. 1H NMR (acetoneꢀd6),
: 1.45 (d, 3 H, CHMe, J = 9.0 Hz); 1.49 (s, 9 H, CMe3); 4.57
(m, 1 H, CHMe); 4.86 (m, 1 H, ꢀHCp); 4.91 (m, 1 H, ´ꢀHCp);
5.13 (m, 0.3 H, ꢀHCp); 5.17 (m, 0.7 H, ´ꢀHCp); 6.32 (br.d,
1 H, NH, J = 12.0 Hz).
2ꢀ[1ꢀ(tertꢀButoxycarbonylamino)ethyl]cymantrenecarbaldeꢀ
hydes (2a,b) were obtained according to general procedure I
from compound 1 (1.3 g, 3.7 mmol), BunLi (5 mL, 8 mmol), and
DMF (2.2 mL, 29 mmol). The yield of a dark red oily mixture of
aldehydes 2a,b was 0.3 g (22%). Compound 1 (0.7 g, 54%) was
also recovered. Product 2 is a 3 : 2 mixture of two isomers. Major
J = 7.1 Hz); 1.55 (s, 9 H, CMe3); 2.46 (s, 3 H, NMe); 3.84 (m, 1 H,
ꢀHCp); 4.01 (m, 1 H, ´ꢀHCp); 4.24 (m, 1 H, ꢀHCp); 4.46
(m, 1 H, ´ꢀHCp); 5.38 (q, 1 H, CHMe, J = 7.1 Hz). Minor
conformer. 1H NMR (benzeneꢀd6), : 1.01 (d, 3 H, CHMe,
J = 7.1 Hz); 1.55 (s, 9 H, CMe3); 2.53 (s, 3 H, NMe); 3.84 (m, 1 H,
ꢀHCp); 4.01 (m, 1 H, ´ꢀHCp); 4.17 (m, 1 H, ꢀHCp); 4.52
(m, 1 H, ´ꢀHCp); 5.07 (q, 1 H, CHMe, J = 7.1 Hz). IR
(benzene), /cm–1: 2020 and 1935 both (MnCO), 1694 (C=O).
Found (%): C, 53.77; H, 5.98; N, 3.85; Mn, 14.83.
C16H20MnNO5. Calculated (%): C, 53.18; H, 5.54; N, 3.88;
Mn, 15.24. []D20 –76.9 (c 0.5, EtOH).
NꢀtertꢀButoxycarbonylꢀNꢀmethylꢀ1ꢀcymantrenylꢀ1ꢀdeuteroꢀ
ethylamine (3ꢀD) was obtained according to general procedure I
from compound 3 (1.7 g, 4.6 mmol), BunLi (8 mL, 12.8 mmol),
and D2O (1 mL, 50 mmol). Yield 1.4 g (87.5%), yellow oil. The
product is a 3 : 2 mixture of two conformers. Major conformer.
1H NMR (benzeneꢀd6), : 1.01 (d, 3 H, Me, J = 7.1 Hz); 1.55
(s, 9 H, CMe3); 2.46 (s, 3 H, NMe); 3.84 (m, 1 H, ꢀHCp); 4.01
(m, 1 H, ´ꢀHCp); 4.24 (m, 1 H, ꢀHCp); 4.46 (m, 1 H, ´ꢀHCp).
1
Minor conformer. H NMR (benzeneꢀd6), : 1.01 (d, 3 H, Me,
J = 7.1 Hz); 1.55 (s, 9 H, CMe3); 2.53 (s, 3 H, NMe); 3.84
(m, 1 H, ꢀHCp); 4.01 (m, 1 H, ´ꢀHCp); 4.17 (m, 1 H, ꢀHCp);
4.52 (m, 1 H, ´ꢀHCp).
NꢀtertꢀButoxycarbonylꢀNꢀmethylꢀ1ꢀdeuteroꢀ1ꢀ(deuterocyꢀ
mantrenyl)ethylamine (3ꢀD2) was obtained according to general
procedure I from compound 3 (1.7 g, 4.6 mmol), BunLi (8 mL,
12.8 mmol), and D2O (1 mL, 50 mmol). Yield 1.2 g (70.5%),
yellow oil. The product is a 3 : 2 mixture of two conformers.
1
Major conformer. H NMR (benzeneꢀd6), : 1.01 (d, 3 H, Me,
J = 7.1 Hz); 1.55 (s, 9 H, CMe3); 2.46 (m, 3 H, NMe); 3.84
(m, 0.2 H, ꢀHCp); 4.01 (m, 0.6 H, ´ꢀHCp); 4.24 (m, 1 H, ꢀHCp);
4.46 (m, 0.2 H, ´ꢀHCp). Minor conformer. 1H NMR (benzeneꢀd6),
: 1.01 (d, 3 H, Me, J = 7.1 Hz); 1.55 (s, 9 H, CMe3); 2.53
(s, 3 H, NMe); 3.84 (m, 0.2 H, ꢀHCp); 4.01 (m, 0.6 H, ´ꢀHCp);
4.17 (m, 1 H, ꢀHCp); 4.52 (m, 0.2 H, ´ꢀHCp).
NꢀtertꢀButoxycarbonylꢀNꢀmethylꢀ2ꢀcymantrenylbutanꢀ2ꢀ
ylamine (4) was obtained according to general procedure I from
compound 3 (1.7 g, 4.6 mmol), BunLi (8 mL, 12.8 mmol), and
ethyl iodide (7.8 g, 50 mmol). Yield 1.1 g (62%), m.p. 67–68 C
(hexane). 1H NMR (benzeneꢀd6), : 0.86 (t, 3 H, CH2Me,
J = 7.3 Hz); 1.35 (s, 3 H, CMe); 1.39 (q, 1 H, CH2Me, J = 7.3 Hz);
1.45 (s, 9 H, CMe3); 2.79 (s, 3 H, NMe); 2.88 (m, 1 H, CH2Me);
3.93 (m, 2 H, ꢀHCp); 4.14 (m, 1 H, ´ꢀHCp); 4.76 (m, 1 H,
ꢀHCp). Found (%): C, 55.48; H, 6.22; N, 3.67; Mn, 14.20.
C18H24MnNO5. Calculated (%): C, 55.53; H, 6.17; N, 3.60;
Mn, 14.14.

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
2333
NꢀtertꢀButoxycarbonylꢀNꢀmethylꢀ1ꢀbenzylꢀ1ꢀcymantrenylꢀ
ethylamine (5) was obtained according to general procedure I
from compound 3 (1.7 g, 4.6 mmol), BunLi (8 mL, 12.8 mmol),
and benzyl bromide (3.4 g, 20 mmol). Yield 0.9 g (43%), m.p.
69—70 C (hexane). 1H NMR (benzeneꢀd6), : 1.13 (s, 3 H,
CMe); 1.78 (s, 9 H, CMe3); 2.51 (m, 3 H, NMe); 2.67 (d, 1 H,
CH2Ph, J = 12.9 Hz); 4.39 (br.d, 1 H, CH2Ph, J = 12.9 Hz);
4.41 (m, 2 H, ꢀHCp); 4.77 (m, 2 H, ´ꢀHCp); 7.11—7.25
(m, 5 H, Ph). Found (%): C, 61.21; H, 5.88; N, 2.98; Mn, 12.10.
C23H26MnNO5. Calculated (%): C, 61.20; H, 5.76; N, 3.10;
Mn, 12.20.
4ꢀCymantrenylꢀ3,4ꢀdimethylꢀ5ꢀphenyloxazolidinꢀ2ꢀone (6)
was obtained according to general procedure I from compound 3
(1.7 g, 4.6 mmol), BunLi (8 mL, 12.8 mmol), and benzaldehyde
(2.13 g, 20 mmol). Yield 1.2 g (69%), light yellow oil. 1H NMR
(benzeneꢀd6), : 1.04 (s, 3 H, CMe); 2.86 (s, 3 H, NMe); 3.55
(m, 1 H, HCp); 3.60 (m, 1 H, HCp); 4.28 (m, 1 H, HCp); 4.62 (m, 1 H,
HCp); 6.76 (d, 2 H, Ph, J = 7.1 Hz); 7.00 (m, 3 H, Ph). IR (KBr),
/cm–1: 2035 (CO), 1954 (CO), 1778 (C=O), 1710. Found (%):
C, 55.29; H, 3.95; N, 3.92; Mn, 15.11. C17H15MnNO5. Calcuꢀ
lated (%): C, 55.43; H, 4.08; N, 3.80; Mn, 14.95.
Synthesis of Nꢀ(1ꢀcymantrenylethyl)amides (general proceꢀ
dure). An appropriate acid chloride (15 mmol) was added at
–20 C to a solution of 1ꢀaminoethylcymantrene12 (2.5 g, 10 mmol)
and Et3N (2.8 mL, 20 mmol) in CH2Cl2 (50 mL). The reaction
mixture was warmed to room temperature, stirred for an addiꢀ
tional 2 h, neutralized with 10% aqueous NH4Cl (50 mL), and
stirred for 20 min. The organic layer was separated, washed sucꢀ
cessively with 20% aqueous H3PO4, aqueous NaHCO3, and waꢀ
ter, and dried over MgSO4. The solvent was removed and the
residue was crystallized from hexane. This procedure was used
to obtain compounds 7—9.
Nꢀ(1ꢀCymantrenylethyl)acetamide (7). Yield 1.9 g (83%),
m.p. 91—92 C. 1H NMR (benzeneꢀd6), : 0.96 (d, 3 H, CHMe,
J = 6.6 Hz); 1.65 (s, 3 H, COMe); 3.92 (m, 2 H, ꢀHCp); 4.31
(m, 1 H, ꢀHCp); 4.41 (m, 1 H, ´ꢀHCp); 4.90 (br.s, 1 H, CHMe);
4.90 (br.s, 1 H, NH). 1H NMR (acetoneꢀd6), : 1.37 (d, 3 H,
CHMe, J = 6.8 Hz); 1.88 (s, 3 H, COMe); 4.78 (m, 1 H, HCp);
4.83 (br.p, 1 H, CHMe); 4.86 (m, 1 H, HCp); 5.09 (m, 1 H,
HCp); 7.32 (br.d. 1 H, NH). IR (benzene), /cm–1: 2021 (CO),
1936 (2 CO), 1685 (C=O). UV (benzene), max/nm (/mol–1 cm–1):
331 (1309). Found (%): C, 49.89; H, 4.08; N, 4.75; Mn, 19.00.
C12H12MnNO4. Calculated (%): C, 49.83; H, 4.15; N, 4.84;
Mn, 19.03.
Nꢀ[1ꢀ(ꢀDeuterocymantrenyl)ethyl]acetamide (7ꢀD) was obꢀ
tained as described for 1ꢀD from compound 7 (1.3 g, 4.6 mmol),
BunLi (8 mL, 12.8 mmol), and D2O (1 mL, 50 mmol). Yield 1.1 g
(84.5%), m.p. 90–91 C. 1H NMR (CDCl3), : 1.46 (d, 3 H,
CHMe, J = 6.6 Hz); 2.08 (s, 3 H, COMe); 4.70 (m, 1.5 H,
ꢀHCp); 4.86 (m, 1 H, ꢀHCp); 4.91 (m, 1 H, ´ꢀHCp); 5.05
(m, 1 H, CHMe); 5.53 (br.s, 1 H, NH).
Nꢀ(1ꢀCymantrenylethyl)ꢀNꢀmethylacetamide (10). A 60%
suspension of NaH (170 mg, 4.2 mmol) was added in portions
under argon at 0 C to a stirred solution of compound 7 (0.4 g,
1.4 mmol) in DMF (15 mL). The mixture was kept at this temꢀ
perature for 30 min. Then methyl iodide (0.7 mL, 11.2 mmol)
was added dropwise and the reaction mixture was warmed to
~20 C, stirred for 1 h, and poured into ice water (50 mL). The
products were extracted with CH2Cl2 (3×75 mL). The combined
organic extracts were dried over MgSO4 and concentrated.
Compound 10 was isolated by column chromatography (hexꢀ
ane—AcOEt, 4 : 1). Yield 0.35 g (83%), m.p. 75—76 C. 1H NMR
(benzeneꢀd6), : 0.91 (d, 3 H, CHMe, J = 6.5 Hz); 1.76 (s, 3 H,
Me); 2.16 (s, 3 H, NMe); 3.91 (m, 1 H, ꢀHCp); 4.07 (m, 1 H,
´ꢀHCp); 4.31 (m, 1 H, ꢀHCp); 4.54 (m, 1 H, ´ꢀHCp); 5.77
(br.s, 1 H, CHMe). The product is a 7 : 3 mixture of two conꢀ
1
formers. Major conformer. H NMR (CDCl3), : 1.24 (d, 3 H,
CHMe, J = 6.6 Hz); 2.09 (s, 3 H, COMe); 2.79 (s, 3 H, NMe);
4.56 (m, 1 H, ꢀHCp); 4.70 (m, 1 H, ´ꢀHCp); 4.82 (m, 2 H,
ꢀHCp); 5.62 (m, 1 H, CHMe). Minor conformer. 1H NMR
(CDCl3), : 1.29 (d, 3 H, CHMe, J = 6.6 Hz); 2.21 (s, 3 H,
COMe); 2.69 (s, 3 H, NMe); 4.63 (m, 1 H, ꢀHCp); 4.70 (m, 1 H,
´ꢀHCp); 4.82 (m, 2 H, ꢀHCp); 4.82 (m, 1 H, CHMe). Found (%):
C, 51.49; H, 4.62; N, 4.62; Mn, 18.15. C13H14MnNO4. Calcuꢀ
lated (%): C, 51.74; H, 4.49; N, 4.51; Mn, 18.40.
Nꢀ[1ꢀ(ꢀDeuterocymantrenyl)ethyl]ꢀNꢀmethylacetamide
(10ꢀD) was obtained as described for 1ꢀD from compound 10
(1.4 g, 4.6 mmol), a 1.6 M solution of BunLi (8 mL, 12.8 mmol)
in hexane, and D2O (0.1 mL, 5 mmol). Yield 1.2 g (85%), yellow
crystals. 1H NMR (benzeneꢀd6), : 0.91 (d, 3 H, CHMe,
J = 6.5 Hz); 1.76 (s, 3 H, COMe); 2.16 (s, 3 H, NMe); 3.91 (m,
1 H, ꢀHCp); 4.07 (m, 1 H, ´ꢀHCp); 4.31 (m, 0.3 H, ꢀHCp);
4.54 (m, 0.7 H, ´ꢀHCp); 5.77 (br.s, 1 H, CHMe).
Synthesis of cymantrenecarboxamides (general procedure).
A solution of a secondary amine (25 mmol) in CH2Cl2 (10 mL)
was added dropwise under argon at 5 C to a solution of cymanꢀ
trenecarbonyl chloride26 (2.7 g, 10 mmol) in CH2Cl2 (50 mL).
Then the reaction mixture was warmed to ~20 C, stirred for
10—15 min, washed with 2 N HCl and water, and dried over
MgSO4. The solvent was removed and the solid residue was
crystallized from hexane. This procedure was used to obtain comꢀ
pounds 11—13.
N,NꢀDimethylcymantrenecarboxamide (11). Yield 2.4 g (87%),
m.p. 75—76 C. 1H NMR (CDCl3), : 3.10 (s, 6 H, NMe2); 4.74
(m, 2 H, ꢀHCp); 5.27 (m, 2 H, ꢀHCp). MS, m/z (Irel (%)): 275
[M]+ (3), 192 [M – 3CO]+ (6), 191 [M – 3CO]+ (55). Found (%):
C, 48.86; H, 3.83; N, 5.67; Mn, 20.20. C11H10MnNO4. Calcuꢀ
lated (%): C, 48.62; H, 3.66; N, 5.89; Mn, 20.00.
Nꢀ(1ꢀCymantrenylethyl)benzamide (8). Yield 3.1 g (87%),
m.p. 83—84 C. 1H NMR (benzeneꢀd6), : 1.06 (d, 3 H, CHMe,
J = 6.6 Hz); 3.88 (m, 2 H, ꢀHCp); 4.30 (m, 1 H, ꢀHCp); 4.33
(m, 1 H, ´ꢀHCp); 5.19 (m, 1 H, CHMe); 5.83 (m, 1 H, NH);
7.19 (m, 5 H, Ph). IR (benzene), /cm–1: 2019 (CO), 1938
(2 CO), 1672 (C=O). UV (benzene), max/nm (/mol–1 cm–1): 332
(1697). Found (%): C, 58.31; H, 3.94; N, 4.02; Mn, 16.10.
C17H14MnNO4. C, 58.12; H, 3.99; N, 3.99; Mn, 16.61.
Nꢀ(1ꢀCymantrenylethyl)pivalamide (9). Yield 3.0 g (89%),
m.p. 71—72 C. 1H NMR (benzeneꢀd6), : 1.07 (d, 3 H, CHMe,
J = 6.6 Hz); 1.22 (s, 9 H, CMe3); 3.96 (m, 1 H, ꢀHCp); 3.97
(m, 1 H, ´ꢀHCp); 4.28 (m, 1 H, ꢀHCp); 4.44 (m, 1 H, ´ꢀHCp);
N,NꢀDiethylcymantrenecarboxamide (12). Yield 2.7 g (90%),
m.p. 60—61 C. 1H NMR (CDCl3), : 1.17 (t, 6 H, 2 Me,
J = 6.9 Hz); 3.40 (p, 4 H, NCH2, J = 6.9 Hz); 4.70 (m, 2 H,
ꢀHCp); 5.20 (m, 2 H, ꢀHCp). MS, m/z (Irel (%)): 303 [M]+ (3),
220 [M – 3CO]+ (12), 219 [M – 3CO]+ (70). Found (%):
C, 51.34; H, 4.69; N, 4.68; Mn, 18.35. C13H14MnNO4. Calcuꢀ
lated (%): C, 51.50; H, 4.65; N, 4.62; Mn, 18.12.
5.01 (m, 1 H, CHMe); 5.52 (m, 1 H, NH). IR (benzene), /cm–1
:
2017 (CO), 1938 (2 CO), 1673 (C=O). UV (benzene), max/nm
(/mol–1 cm–1): 339 (2089). Found (%): C, 54.33; H, 5.35;
N, 4.12; Mn, 15.80. C15H18MnNO4. Calculated (%): C, 54.38;
H, 5.44; N, 4.23; Mn, 15.67.

2334
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
Kelbysheva et al.
NꢀMethylꢀNꢀphenylcymantrenecarboxamide (13). Yield 3.1 g
(93%), m.p. 73—74 C. 1H NMR (CDCl3), : 3.32 (s, 3 H, NMe);
4.45 (m, 2 H, ꢀHCp); 4.53 (m, 2 H, ꢀHCp); 7.22 (m, 2 H,
NPh); 7.41 (m, 3 H, NPh). MS, m/z (Irel (%)): 337 [M]+ (1), 254
[M – 3CO]+ (15), 253 [M – 3CO]+ (85). Found (%): C, 57.14;
H, 3.62; N, 4.29; Mn, 16.02. C16H12MnNO4. Calculated (%):
C, 56.99; H, 3.59; N, 4.15; Mn, 16.32.
Metalation of N,Nꢀdimethylcymantrenecarboxamide (11).
A reaction of compound 11 (1.4 g, 5.0 mmol) with BunLi (8 mL,
12.8 mmol) and D2O (1 mL, 50 mmol) was carried out accordꢀ
ing to general procedure I. The reaction products were isolated
by column chromatography on silica gel with benzene as an
eluent. This reaction afforded compounds 14, 15, 16a, 17a,
and 11ꢀD.
Butyl cymantrenyl ketone (14). Yield 0.11 g (7.6%), oil,
Rf 0.83. 1H NMR (CDCl3), : 0.92 (t, 3 H, Me, J = 6.7 Hz); 1.32
(m, 2 H); 1.65 (m, 2 H, CH2); 2.52 (br.m, 2 H, CH2CO); 4.79
(m, 2 H, HCp); 5.38 (m, 2 H, HCp). MS, m/z (Irel (%)): 288 [M]+
(3), 204 [M – 3CO]+ (55). Found (%): C, 54.25; H, 4.31;
Mn, 18.9. C13H13MnO4. Calculated (%): C, 54.18; H, 4.55;
Mn, 19.06.
1,1ꢀDibutylꢀ1ꢀcymantrenylmethanol (15). Yield 0.035 g
(2.4%), Rf 0.75.
N,NꢀDiethylꢀ2ꢀ(cymantrenylcarbonyl)cymantrenecarboxꢀ
amide (16b). Yield 0.085 g (3.2%), m.p. 127—128 C, Rf 0.62.
1H NMR (CDCl3), : 1.07 (t, 3 H, Me, J = 6.7 Hz); 1.19 (t, 3 H,
Me, J = 6.7 Hz); 3.22 (m, 3 H, NCH2); 3.62 (m, 1 H, NCH2);
4.67 (m, 1 H, HCp); 4.88 (m, 1 H, HCp); 4.89 (m, 1 H, HCp); 5.20
(m, 1 H, HCp); 5.34 (m, 1 H, HCp); 5.53 (m, 2 H, HCp). MS, m/z
(Irel (%)): 449 [M – 3CO]+ (22), 365 [M – 6CO]+ (35). Found (%):
C, 49.84; H, 3.45; Mn, 20.35; N, 4.46. C22H17Mn2NO8. Calcuꢀ
lated (%): C, 49.55; H, 3.21; Mn, 20.63; N, 2.63.
N,NꢀDiethylꢀ2ꢀ(1ꢀcymantrenylꢀ1ꢀhydroxypentyl)cymantreꢀ
necarboxamide (17b). Yield 0.23 g (7.7%), m.p. 141—142 C,
Rf 0.5. 1H NMR (CDCl3), : 0.97 (t, 3 H, Me, J = 7.2 Hz); 1.19
(t, 6 H, 2 Me, J = 6.8 Hz); 1.37 (m, 2 H, CH2); 1.50—2.0
(m, 4 H, 2 CH2); 3.27 (br.m, 2 H, NCH2); 3.47 (m, 2 H, NCH2);
4.41 (m, 1 H, HCp); 4.45 (m, 1 H, HCp); 4.50 (m, 1 H, HCp); 4.67
(m, 0.6 H, HCp); 4.94 (m, 0.7 H, HCp); 4.98 (m, 2 H, HCp); 6.77
(br.s, 1 H, OH). MS, m/z (Irel (%)): 509 [M – 3CO]+ (35), 508
[M – 3CO]+ (70), 507 [M – 3CO]+ (35), 491 [M – 3CO –
– H2O]+ (20), 490 [M – 3CO – H2O]+ (40), 489 [M – 3CO –
–H2O]+ (20). Found (%): C, 52.75; H, 4.05; Mn, 18.22; N, 2.47.
C26H27Mn2NO8. Calculated (%): C, 52.81; H, 4.60; Mn, 18.58;
N, 2.37.
1,1ꢀDibutylꢀ1ꢀcymantrenylmethanol (15). Yield 0.8 g (4.8%),
1
Rf 0.75. H NMR (CDCl3), : 0.90 (t, 6 H, 2 Me, J = 6.6 Hz);
1.29—1.35 (m, 8 H, 4 CH2); 1.64 (m, 4 H, 2 CH2); 4.60 (m, 1.7 H,
ꢀHCp); 4.86 (m, 1.4 H, ꢀHCp). MS, m/z (Irel (%)): 263
[M – 3 CO]+ (15), 262 [M – 3 CO]+ (7), 245 [M – 6 CO –
– H2O]+ (85), 245 [M – 6 CO – H2O]+ (41). Found (%):
C, 54.25; H, 4.31; Mn, 18.9. C17H23MnO4. Calculated (%):
C, 58.96; H, 6.69; Mn, 15.86.
N,NꢀDiethylꢀꢀdeuterocymantrenecarboxamide (12ꢀD). Yield
1.23 g (82.3%), Rf 0.39. 1H NMR (CDCl3), : 1.17 (t, 6 H,
CH2Me, J = 6.9 Hz); 3.40 (p, 4 H, CH2Me, J = 6.9 Hz); 4.70
(m, 1.8 H, ꢀHCp); 5.20 (m, 0.2 H, ꢀHCp). MS, m/z (Irel (%)):
220 [M – 3CO]+ (58), 219 [M – 3CO]+ (17).
N,NꢀDimethylꢀ2ꢀ(cymantrenylcarbonyl)cymantrenecarboxꢀ
amide (16a). Yield 1.5 g (64%), m.p. 157—158 C, Rf 0.6.
1H NMR (CDCl3), : 2.90 (s, 3 H, NMe2); 3.04 (s, 3 H, NMe2);
4.70 (m, 1 H, HCp); 4.93 (m, 2 H, HCp); 5.23 (m, 1 H, HCp); 5.37
(m, 1 H, HCp); 5.50 (m, 1 H, HCp); 5.55 (m, 2 H, HCp). MS, m/z
(Irel (%)): 421 [M – 3CO]+ (83), 337 [M – 6CO]+ (85).
Found (%): C, 47.75; H, 2.76; N, 3.01. C20H13Mn2NO8. Calcuꢀ
lated (%): C, 47.55; H, 2.59; N, 2.77.
N,NꢀDimethylꢀ2ꢀ(1ꢀcymantrenylꢀ1ꢀhydroxypentyl)cymanꢀ
trenecarboxamide (17a). Yield 0.13 g (5%), m.p. 136—137 C,
Rf 0.53. 1H NMR (CDCl3), : 0.96 (t, 3 H, Me, J = 7.2 Hz); 1.40
(m, 2 H, CH2); 1.5—2.0 (m, 4 H, 2 CH2); 2.95 (s, 3 H, NMe);
3.02 (s, 3 H, NMe); 4.40 (m, 1 H, HCp); 4.47 (m, 2 H, HCp);
4.65 (m, 1 H, HCp); 4.91 (m, 1 H, HCp); 4.97 (m, 2 H, HCp); 6.72
(br.s, 1 H, OH). MS, m/z (Irel (%)): 480 [M – 3CO]+ (3), 479
[M – 3 CO]+ (10), 378 [M – 6 CO – H2O]+ (11), 377 [M –
– 6 CO – H2O]+ (43), 489 [M – 3 CO – H2O]+ (20). Found (%):
C, 50.92; H, 4.22; Mn, 19.8; N, 2.29. C24H23Mn2NO8. Calcuꢀ
lated (%): C, 51.17; H, 4.12; Mn, 19.51; N, 2.49.
N,NꢀDimethylꢀꢀdeuterocymantrenecarboxamide 11ꢀD.
Yield 0.23 g (16.4%), Rf 0.41. 1H NMR (CDCl3), : 3.10 (s, 6 H,
NMe2); 4.74 (m, 1.8 H, ꢀHCp); 5.27 (m, 0.2 H, ꢀHCp). MS,
m/z (Irel (%)): 192 [M – 3CO]+ (83), 191 [M – 3CO]+ (25).
Metalation of N,Nꢀdiethylcymantrenecarboxamide (12).
A (direct order of addition of the reagents). A reaction of comꢀ
pound 12 (1.5 g, 5.0 mmol) with BunLi (8 mL, 12.8 mmol)
and D2O (1 mL, 50 mmol) was carried out according to generꢀ
al procedure I. The reaction products were isolated by colꢀ
umn chromatography on silica gel with benzene as an
eluent. This reaction afforded compounds 14, 15, 16b, 17b,
and 12ꢀD.
B (reverse order of addition of the reagents). The reaction was
carried out by adding a solution of compound 12 (1.5 g, 5.0 mmol)
in THF (10 mL) to a solution of BunLi (8 mL, 12.8 mmol) in
THF (50 mL), whereupon D2O (1 mL, 5.0 mmol) was added.
The reaction products were isolated by column chromatography
on silica gel with benzene as an eluent. The yields of compounds
14, 15, 16b, 17b, and 12ꢀD were 0.12 g (8.7%), 0.11 g (7.5%),
0.35 g (13.2%), 0.52 g (17.6%), and 0.63 g (42.1%), respectively.
Metalation of NꢀmethylꢀNꢀphenylcymantrenecarboxamide
(13). A (direct order of addition of the reagents). A reaction of
compound 13 (1.7 g, 5 mmol) with BunLi (8 mL, 12.8 mmol)
and D2O (1 mL, 5 mmol) was carried out according to general
procedure I. The reaction products were isolated by column
chromatography on SiO2 with benzene as an eluent. This reacꢀ
tion afforded compounds 14 (0.56 g, 39%; Rf 0.83), 15 (0.08 g,
5.6%; Rf 0.75), 16c, 17c, and 13ꢀD.
NꢀMethylꢀNꢀphenylꢀ2ꢀ(cymantrenylcarbonyl)cymantreneꢀ
carboxamide (16c). Yield 0.11 g (4.2%), m.p. 137—138 C,
Rf 0.59. 1H NMR (CDCl3), : 3.04 (s, 3 H, NMe2); 4.67 (m, 1 H,
HCp); 4.88 (m, 1 H, HCp); 4.90 (m, 1 H, HCp); 5.21 (m, 1 H,
HCp); 5.34 (m, 1 H, HCp); 5.54 (m, 1 H, HCp); 5.55 (m, 2 H,
HCp); 7.10—7.37 (m, 5 H, Ph). MS, m/z (Irel (%)): 483 [M –
– 3 CO]+ (53), 399 [M – 6CO]+ (65). Found (%): C, 52.81;
H, 2.87; Mn, 19.7; N, 2.38. C25H15Mn2NO8. Calculated (%):
C, 52.93; H, 2.67; Mn, 19.37; N, 2.47.
NꢀMethylꢀNꢀphenylꢀ2ꢀ(1ꢀcymantrenylꢀ1ꢀhydroxypentyl)ꢀ
cymantrenecarboxamide (17c). Yield 0.23 g (7.2%), m.p.
152—153 C, Rf 0.52. 1H NMR (CDCl3), : 0.97 (t, 3 H, Me,
J = 7.2 Hz); 1.38 (m, 2 H, CH2); 1.60 (m, 1 H, CH2); 1.91
(m, 3 H, CH2); 3.38 (s, 3 H, NMe); 3.95 (m, 1 H, HCp); 4.06
(m, 1 H, HCp); 4.50 (m, 1 H, HCp); 4.62 (m, 1 H, HCp); 4.79
(m, 2 H, HCp); 5.11 (m, 1 H, HCp); 6.84 (m, 2 H, Ph); 7.66 (m, 3 H,
Butyl cymantrenyl ketone (14). Yield 0.03 g (2.2%), Rf 0.83.

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
2335
Ph); 7.66 (s, 1 H, OH). MS, m/z (Irel (%)): 542 [M – 3 CO]+ (3),
541 [M – 3 CO]+ (8), 440 [M – 6CO – H2O]+ (3), 439 [M –
– 6 CO – H2O]+ (10). Found (%): C, 55.47; H, 3.87; Mn, 17.72;
N, 2.18. C29H25Mn2NO8. Calculated (%): C, 55.69; H, 4.03;
Mn, 17.57; N, 2.27.
NꢀMethylꢀNꢀphenylꢀꢀdeuterocymantrenecarboxamide 13ꢀD.
Yield 0.72 g (42%), Rf 0.37. 1H NMR (CDCl3), : 3.32 (s, 3 H,
NMe); 4.45 (m, 1.8 H, ꢀHCp); 4.53 (m, 0.2 H, ꢀHCp); 7.22
(m, 2 H, NPh); 7.41 (m, 3 H, NPh). MS, m/z (Irel (%)): 254
[M – 3 CO]+ (65), 253 [M – 3 CO]+ (11).
B (reverse order of addition of the reagents). The reaction was
carried out by adding a solution of compound 13 (1.7 g, 50 mmol)
in THF (10 mL) to a solution of BunLi (8 mL, 12.8 mmol) in
THF (50 mL), whereupon D2O (1 mL, 5.0 mmol) was added.
The reaction products were isolated by column chromatography
on silica gel with benzene as an eluent. The yields of compounds
14, 15, 17c, and 13ꢀD were 0.25 g (17%), 0.04 g (3%), 0.11 g
(3%), and 1.3 g (76.2%), respectively.
Reduction of amides 11ꢀD—13ꢀD (general procedure). A soluꢀ
tion of amide 11ꢀD—13ꢀD (1 mmol) in dry THF (5 mL) was
added dropwise under argon at 7—9 C to a 1.4 M solution of
BH3 (1.42 mL) in THF. The reaction was heated to 35 C, kept
for 2 h, and refluxed with 6 M HCl (15 mL) for 1 h. Then Et2O
(50 mL) was added and the mixture was alkalified with 2 M
NaOH to pH 8. The product was extracted with diethyl ether.
The combined extracts were washed with water, dried over
MgSO4, and concentrated. Products 18a—c were purified by
column chromatography on SiO2 with AcOEt as an eluent.
Deuteroꢀ1ꢀ(N,Nꢀdimethylaminomethyl)cymantrene3 (18a).
Yield 0.22 g (78%), oil. 1H NMR (CDCl3), : 2.23 (s, 6 H,
2 Me); 3.04 (s, 2 H, CH2); 4.65 (m, 2 H, ꢀHCp); 4.69 (m, 1.3 H,
ꢀHCp). MS, m/z (Irel (%)): 178 [M – 3CO]+ (65), 177 [M –
– 3 CO]+ (16).
aqueous HCl was added and the reaction mixture was washed
with CHCl3. The aqueous layer was alkalified with 10 M NaOH
to pH 9 and the product was extracted with Et2O. The combined
organic layers were dried over MgSO4 and concentrated. The
product obtained was purified by column chromatography on
SiO2 with AcOEt as an eluent.
2ꢀDeuteroꢀ1ꢀ(N,Nꢀdimethylaminomethyl)cymantrene3 (18aꢀD).
Yield 0.8 g (31%). The spectral characteristics of the product
obtained are identical with those cited above for compound 18a.
2ꢀDeuteroꢀ1ꢀ(N,Nꢀdiethylaminomethyl)cymantrene (18bꢀD).
Yield 1.2 g (42%). The spectral characteristics of the product
obtained are identical with those cited above for compound 18b.
2ꢀDeuteroꢀ1ꢀ(NꢀmethylꢀNꢀphenylaminomethyl)cymantrene
(18cꢀD). Yield 1.6 g (49%). The spectral characteristics of the
product obtained are identical with those cited above for comꢀ
pound 18c.
NꢀAllylꢀN´ꢀ(1ꢀcymantrenylethyl)ꢀNꢀphenylurea (21). Step 1.
Phenyl isocyanate (1.6 mL, 14.6 mmol) was added to a solution
of 1ꢀcymantrenylethylamine (3.0 g, 12.2 mmol) in dry THF
(100 mL). After 1 h, the solvent was removed in vacuo and the
residue was crystallized from hexane—ethyl acetate (3 : 1). The
yield of Nꢀ(1ꢀcymantrenylethyl)ꢀN´ꢀphenylurea (30) was 3.3 g
1
(75%), m.p. 90—91 C. H NMR (acetoneꢀd6), : 1.47 (d, 3 H,
Me, J = 7.0 Hz); 4.87 (m, 1 H, CHN); 4.89 (m, 1 H, HCp); 4.94
(m, 1 H, HCp); 5.16 (m, 2 H, HCp); 5.98 (d, 1 H, NH, J = 7.7 Hz);
6.97 (t, 1 H, Ph, J = 7.4 Hz); 7.28 (t, 2 H, Ph, J = 7.7 Hz); 7.53
(d, 2 H, Ph, J = 7.8 Hz); 8.00 (s, 1 H, NH). Found (%): C, 56.85;
H, 4.69; Mn, 14.9; N, 7.05. C17H15MnN2O4•1/6C6H14. Calcuꢀ
lated (%): C, 55.75; H, 4.13; Mn, 15.00; N, 7.65.
Step 2. A 60% suspension of NaH (0.2 g, 4.1 mmol) was
added in portions under argon at 0 C to a stirred solution of
compound 30 (1.0 g, 2.7 mmol) in DMF (15 mL). The mixture
was kept at 0 C for 30 min, whereupon allyl bromide (0.4 mL,
4.1 mmol) was added dropwise. The reaction mixture was stirred
at ~20 C for 1 h and then poured into ice water (50 mL). The
product was extracted with CH2Cl2 (3×75 mL). The combined
organic extracts were dried over MgSO4 and concentrated. The
product was purified by column chromatography with hexane—
AcOEt (4 : 1) as an eluent. The yield of compound 21 was 0.9 g
Deuteroꢀ1ꢀ(N,Nꢀdiethylaminomethyl)cymantrene (18b). Yield
0.23 g (80%), b.p. 80—82 C (0.08 Torr). 1H NMR (CDCl3),
: 1.03 (t, 6 H, Me, J = 6.1 Hz); 2.50 (p, 4 H, CH2, J = 6.1 Hz);
3.24 (s, 2 H, NCH2); 4.65 (m, 2 H, ꢀHCp); 4.71 (m, 1.3 H,
ꢀHCp). Found (%): C, 54.30; H, 4.62; N, 4.89; Mn, 18.75.
C13H16NO3Mn. Calculated (%): C, 53.99; H, 5.58; N, 4.84;
Mn, 19.02. MS, m/z (Irel (%)): 206 [M – 3CO]+ (46), 205
[M – 3 CO]+ (16).
1
(82%), yellow oil. H NMR (acetoneꢀd6), : 1.34 (d, 3 H, Me,
J = 6.8 Hz); 4.33 (d, 2 H, CH2CH=, J = 5.9 Hz); 4.84 (m, 1 H,
HCp); 4.89 (m, 1 H, CH); 4.90 (m, 1 H, HCp); 5.01 (m, 1 H,
HCp); 5.06 (m, 1 H, HCp); 5.09 (dm, 1 H, =CH2); 5.13 (dm, 1 H,
=CH2); 5.98 (m, 1 H, =CH); 7.33—7.48 (m, 5 H, Ph); 8.02 (s, 1 H,
NH). Found (%): C, 58.78; H, 5.34; N, 6.91. C20H19MnN2O4.
Calculated (%): C, 59.12; H, 4.71; N, 6.89.
Deuteroꢀ1ꢀ(NꢀmethylꢀNꢀphenylaminomethyl)cymantrene (18c).
Yield 0.26 g (82%), m.p. 70—71 C (hexane). 1H NMR (CDCl3),
: 2.98 (s, 3 H, NMe); 4.16 (s, 2 H, CH2); 4.63 (m, 2 H, ꢀHCp);
4.73 (m, 1.4 H, ꢀHCp); 6.81 (m, 3 H, Ph); 7.29 (m, 2 H, Ph).
Found (%): C, 59.53; H, 4.48; N, 4.15; Mn, 16.89. C16H14NO3Mn.
Calculated (%): C, 59.45; H, 4.37; N, 4.37; Mn, 16.99. MS, m/z
(Irel (%)): 240 [M – 3CO]+ (100), 239 [M – 3CO]+ (44).
1ꢀChloromethylꢀ2ꢀdeuterocymantrene (20) was obtained by
bubbling gaseous HCl through a solution of 10 g (43 mmol)
ꢀdeuterocymantrenylmethanol (19)3,4 in dry CH2Cl2 (25 mL)
at 10 C for 30 min. The reaction mixture was dried over MgSO4
and concentrated in vacuo, and the residue was distilled. Yield
NꢀAllylꢀN´ꢀ[1ꢀ(2ꢀallylcymantrenyl)ethyl]ꢀNꢀphenylurea (22)
was obtained according to general procedure I from compound
21 (2.0 g, 4.9 mmol), BunLi (9 mL, 14.8 mmol), and allyl bromide
(1.0 mL, 14.8 mmol). Major diastereomer (first fraction, yellow
1
oil). Yield 0.8 g (36%). H NMR (acetoneꢀd6), : 1.30 (d, 3 H,
Me, J = 6.8 Hz); 3.06 (ddm, 1 H, CH2, J = 16.0 Hz, J = 6.0 Hz);
3.18 (ddm, 1 H, CH2, J = 16.1 Hz, J = 7.3 Hz); 4.29 (ddm, 1 H,
CH2, J = 15.6 Hz, J = 6.0 Hz); 4.56 (ddm, 1 H, CH2, J = 15.6 Hz,
J = 5.6 Hz); 4.65 (m, 1 H, HCp); 4.72 (m, 1 H, HCp); 4.84 (br.m,
1 H, NCH); 4.90 (m, 1 H, HCp); 4.99 (br.d, 1 H, NH, J = 8.2 Hz);
5.03 (dm, 1 H, CH2, J= 10.2 Hz); 5.06 (dm, 1 H, CH2, J = 17.2 Hz);
5.10 (dm, 1 H, CH2, J = 9.7 Hz); 5.16 (dm, 1 H, CH2,
J = 17.1 Hz); 5.92 (m, 1 H, =CH); 7.33 (m, 3 H, Ph); 7.42
(m, 2 H, Ph). 13C NMR (acetoneꢀd6), : 22.46 (Me); 30.48
(CH); 42.37 (CH2); 51.95 (CH2); 78.38 (Cp); 81.80 (Cp); 82.83
9.5 g (87%), b.p. 40—41 C (2•10–2 Torr), nD 1.6085; cf.
20
Ref. 27: b.p. 35—36 C (1.5•10–2 Torr). 1H NMR (CDCl3),
: 4.21 (s, 2 H, CH2); 4.69 (m, 2 H, ꢀHCp); 4.89 (m, 1 H, ꢀHCp).
MS, m/z (Irel (%)): 254 [M – 3CO]+ (15), 253 [M – 3CO]+ (85).
Synthesis of ꢀdeuterated analogs of amines 18a—c from comꢀ
pound 20 (general procedure). A mixture of compound 20 (2.5 g,
10 mmol) and a solution of an appropriate amine (25 mmol) in
CHCl3 (50 mL) was refluxed on a water bath for 40 h. Then

2336
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
Kelbysheva et al.
(Cp); 103.77 (C1Cp); 107.45 (C1Cp); 115.89 (CH2=); 116.69
(CH2=); 127.17 (Ph); 128.40 (Ph); 129.74 (Ph); 135.30 (CH=);
135.53 (CH=); 142.02 (C1Ph); 156.00 (CO); 225.32 (3 CO).
Found (%): C, 61.97; H, 5.39; Mn, 12.25; N, 6.18. C23H23MnN2O4.
Calculated (%): C, 61.89; H, 5.19; Mn, 12.31; N, 6.27. Minor
diastereomer (second fraction, yellow oil). Yield 0.6 g (27%).
1H NMR (acetoneꢀd6), : 1.36 (d, 3 H, Me, J = 6.6 Hz); 3.06
(dd, 1 H, CH2, J = 16.0 Hz, J = 6.4 Hz); 3.22 (dd, 1 H, CH2,
J = 15.6 Hz, J = 6.4 Hz); 4.23 (m, 2 H, CH2); 4.56 (m, 1 H, HCp);
4.83 (m, 1 H, HCp); 4.91 (br.m, 1 H, NCH); 5.01 (m, 1 H, HCp);
5.05—5.21 (m, 4 H, 2 CH2=); 5.37 (br.d, 1 H, NH, J = 8.4 Hz);
5.77—5.95 (m, 2 H, 2 CH=); 7.24 (m, 3 H, Ph); 7.40 (m, 2 H,
Ph). 13C NMR (acetoneꢀd6), : 19.95 (Me), 30.36 (CH), 42.07
(CH2), 52.01 (CH2), 76.47 (Cp), 83.90 (Cp), 84.40 (Cp), 103.95
(C1Cp), 105.02 (C1Cp), 115.86 (CH2=), 116.33 (CH2=), 126.95
(Ph), 128.33 (Ph), 129.58 (Ph), 135.27 (CH=), 135.87 (CH=),
142.11 (C1Ph), 155.50 (CO), 225.56 (3 CO).
Nꢀ(1ꢀCymantrenylethyl)ꢀN,N´ꢀdimethylꢀN´ꢀphenylurea (23)
was obtained as described for the synthesis of compound 21 from
(1ꢀureidoethyl)cymantrene 30 (1.2 g, 3.3 mmol), a 60% suspenꢀ
sion of NaH (0.3 g, 4.9 mmol), and methyl iodide (0.4 mL,
6.4 mmol). The product was purified by column chromatography
with hexane—AcOEt (4 : 1) as an eluent. Yield 0.91 g (69%),
m.p. 95—96 C. 1H NMR (acetoneꢀd6), : 1.27 (d, 3 H, Me,
J = 6.7 Hz); 2.32 (s, 3 H, MeN); 3.15 (s, 3 H, MeN); 4.78 (m, 1 H,
HCp); 4.98 (m, 1 H, HCp); 5.04 (m, 1 H, HCp); 5.06 (br.p, 1 H,
CH, J = 6.8 Hz); 5.16 (m, 1 H, HCp); 7.14 (tm, 1 H, Ph, J = 7.4 Hz);
7.17 (dm, 2 H, Ph, J = 7.5 Hz); 7.37 (tm, 2 H, Ph, J = 7.4 Hz).
Found (%): C, 57.85; H, 4.77; Mn, 13.7; N, 6.99. C19H19MnN2O4.
Calculated (%): C, 57.87; H, 4.86; Mn, 13.93; N, 7.11.
(16 mL, 30 mmol), and DMF (2.5 mL, 30 mmol). Compound 28.
Yield 1.5 g (35%), oil. 1H NMR (acetoneꢀd6), : 4.16 (dm, 2 H,
CH2, J = 5.5 Hz); 4.51 (d, 1 H, OCH2, J = 12.7 Hz); 4.59 (d, 1 H,
OCH2, J = 12.7 Hz); 5.12 (m, 1 H, HCp); 5.20 (dm, 2 H, CH2,
J = 10.5 Hz); 5.26 (m, 1 H, HCp); 5.34 (dm, 1 H, =CH2,
J = 17.3 Hz); 5.68 (m, 1 H, HCp); 5.96 (dddd, 1 H, =CH,
J = 17.3 Hz, J = 10.5 Hz, J = 6.4 Hz, J = 1.4 Hz); 9.84 (s, 1 H,
CHO). 13C NMR (acetoneꢀd6), : 65.12 (CH2); 72.07 (CH2O);
83.05 (Cp); 85.33 (Cp); 88.13 (Cp); 90.14 (C1Cp); 107.76 (C1Cp);
116.77 (CH2=); 135.02 (CH=); 188.48 (CHO); 223.49 (3 CO).
Found (%): C, 51.36; H, 3.52; Mn, 18.5. C13H11MnO5. Calcuꢀ
lated (%): C, 51.67; H, 3.68; Mn, 18.18. Compound 29. Yield 0.8 g
(17%), oil. 1H NMR (acetoneꢀd6), : 4.10 (dm, 2 H, CH2,
J = 5.3 Hz); 4.23 (s, 2 H, OCH2); 5.25 (dm, 1 H, =CH2,
J = 10.5 Hz); 5.27 (m, 1 H, HCp); 5.33 (dm, 1 H, =CH2,
J = 17.2 Hz); 5.66 (m, 1 H, HCp); 5.76 (m, 1 H, HCp); 5.93
(dddd, 1 H, =CH, J = 17.2 Hz, J = 10.5 Hz, J = 6.7 Hz,
J = 1.4 Hz); 9.64 (s, 1 H, CHO). 13C NMR (acetoneꢀd6), : 65.13
(CH2); 71.84 (CH2O); 85.20 (Cp); 86.58 (Cp); 87.05 (Cp); 91.21
(C1Cp); 104.87 (C1Cp); 116.64 (CH2=); 135.02 (CH=); 187.84
(CHO); 223.47 (3 CO).
Xꢀray diffraction study of complexes 17b´ and 17bІІІ. Crysꢀ
tallographic parameters and the data collection and refinement
statistics for compounds 17b´ and 17b are summarized in Table 3.
Experimental reflection intensities were measured with a SMART
APEX II diffractometer28 (graphite monochromator, MoꢀK
radiation,  = 0.71073 Å,  scan mode). An absorption correcꢀ
tion was applied semiempirically with the SADABS program.29
The structures were solved by direct methods and refined anisoꢀ
Nꢀ(2ꢀCymantrenylpentꢀ4ꢀenꢀ2ꢀyl)ꢀN,N´ꢀdimethylꢀN´ꢀphenylꢀ
urea (24) was obtained according to general procedure I from
compound 23 (0.51 g, 1.3 mmol), BunLi (3 mL, 2.6 mmol), and
AllBr (0.22 mL, 2.6 mmol). Yield 0.32 g (55%), yellow oil.
1H NMR (acetoneꢀd6), : 2.06 (s, 3 H, Me); 2.76 (s, 3 H, MeN);
2.85 (s, 3 H, MeN); 3.79 (m, 2 H, CH2); 4.67 (m, 1 H, HCp);
Table 3. Crystallographic parameters and the data collection and
refinement statistics for structures 17b´ and 17b
Parameter
17b´
17b
4.76 (m, 1 H, HCp); 5.06 (m, 1 H, HCp); 5.11 (m, 1 H, HCp
,
Molecular formula
Molecular weight
Crystal system
Space group
Temperature, K
a/Å
b/Å
c/Å
/deg
/deg
C26H27Mn2NO8 C26H27Mn2NO8
J = 10.2 Hz); 5.16 (m, 1 H, HCp, J = 16.9 Hz); 5.16 (dm, 1 H,
CH2); 5.47 (m, 1 H, HCp); 5.74 (m, 1 H, =CH); 7.18 (tm, 1 H,
Ph, J = 7.4 Hz); 7.31 (m, 2 H, Ph); 7.49 (dm, 2 H, Ph, J = 7.6 Hz).
Allylcymantrene (25) was obtained according to general proꢀ
cedure I from cymantrene (4.1 g, 20 mmol), BunLi (18 mL,
30 mmol), and AllBr (2.6 mL, 30 mmol). Yield 2.1 g (43%), b.p.
100—102 C (10 Torr). 1H NMR (CDCl3), : 3.02 (dm, 2 H,
CH2, J = 6.7 Hz); 4.63 (m, 2 H, HCp); 4.65 (m, 2 H, HCp);
5.05—5.17 (m, 2 H, =CH2); 5.85 (m, 1 H, =CH). Found (%):
C, 54.21; H, 3.83; Mn, 22.3. C11H9MnO4. Calculated (%):
C, 54.12; H, 3.72; Mn, 22.50.
3ꢀAllylcymantrenecarbaldehyde (26) was obtained according
to general procedure I from compound 25 (1.6 g, 6.5 mmol),
BunLi (9 mL, 14.8 mmol), and DMF (1.2 mL, 16.4 mmol). Yield
0.4 g (24%), oil. 1H NMR (acetoneꢀd6), : 3.16 (m, 2 H, CH2);
5.15 (dm, 1 H, =CH2, J = 10.1 Hz); 5.19 (m, 1 H, HCp); 5.22
(dm, 1 H, =CH2, J = 16.9 Hz); 5.61 (m, 1 H, HCp); 5.71 (m, 1 H,
HCp); 5.95 (dddd, 1 H, =CH, J = 16.9 Hz, J = 10.1 Hz, J = 6.8 Hz,
J = 3.3 Hz); 9.65 (s, 1 H, CHO). Found (%): C, 52.82; H, 3.02;
Mn, 19.9. C12H9MnO4. Calculated (%): C, 52.96; H, 3.33;
Mn, 20.19.
591.37
Monoclinic
P21/c
591.37
Monoclinic
P21/c
100(2)
9.750(11)
20.51(3)
12.863(15)
90
100(2)
19.342(13)
10.431(8)
13.486(10)
90
97.51(3)
90
105.122(15)
90
/deg
3
V/Å
2551(5)
4
2627(3)
4
Z
dcalc/g cm–3
2max/deg
/cm–1
1.540
1.495
58
52
10.41
10.10
Number of unique
6775(0.0522)
5162 (0.0213)
reflections (Rint
)
R1 (on F for reflections
with I > 2(I))
0.0397 (5441)
0.0419 (4471)
wR2 (on F2 for all reflections) 0.0993
0.1125
360
Number of
parameters refined
GOOF
341
2ꢀ and 3ꢀAllyloxymethylcymantrenecarbaldehydes (28) and
(29) were obtained according to general procedure I from allylꢀ
oxymethylcymantrene 27 (4.3 g, 15.7 mmol) (see Ref. 15), BunLi
1.013
1.017

Metalation of cymantrene derivatives
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 12, December, 2012
2337
tropically by the fullꢀmatrix leastꢀsquares method on F2hkl for all
nonꢀhydrogen atoms. The H atoms of the hydroxyl group were
located in the difference electronꢀdensity maps; the remaining
H atoms were located geometrically and refined using a riding
model. The terminal part of the butyl substituent (the C(20) and
C(21) atoms) in structure 17b´ is disordered over two positions
with occupancy factors of 60 and 40%. All computerꢀassisted
calculations were performed with the SHELXTL program packꢀ
age.30 Comprehensive tables of atomic coordinates, bond lengths,
bond angles, and anisotropic thermal parameters have been deꢀ
posited with the Cambridge Structural Database.
12. N. M. Loim, M. V. Larukova, V. G. Andrianov, V. A.
Tsiryapkin, Z. N. Parnes, Yu. T. Struchkov, J. Organomet.
Chem., 1983, 248, 73.
13. T. T. To, C. B. Duke, III, C. S. O´Brien, C. R. Ross, II,
C. E. Barnes, C. E. Webster, T. J. Burkey, Organometallics,
2008, 27, 289.
14. L. N. Telegina, M. G. Ezernitskaya, I. A. Godovikov, K. K.
Babievskii, B. V. Lokshin, T. V. Strelkova, Yu. A. Borisov,
N. M. Loim, Organometallics, 2009, 28, 3636.
15. E. S. Kelbysheva, M. G. Ezernitskaya, T. V. Strelkova, Yu. A.
Borisov, A. F. Smol´yakov, Z. A. Starikova, F. M. Dolꢀ
gushin, A. N. Rodionov, B. V. Lokshin, N. M. Loim, Organoꢀ
metallics, 2011, 30, 4342.
16. L. Keller, S. Beaumont, J.ꢀM. Liu, S. Thoret, J. S. Bignon,
J. WdzieczakꢀBakala, P. Dauban, R. H. Dodd, J. Med.
Chem., 2008, 51, 3414.
This work was financially supported by the Presidium
of the Russian Academy of Sciences (Basic Research Proꢀ
gram Pꢀ8 "Development of Methods for the Synthesis of
Chemical Compounds and Design of Novel Materials").
17. J. M. Chong, L. S. Hegedus, Organometallics, 2004, 23, 1010.
18. R. K. Dieter, H. Yu, Org. Lett., 2000, 2, 2283.
19. A. Basu, S. Thayumanavan, Angew. Chem., Int. Ed., 2002,
41, 716.
References
20. K. Nishihata, M. Nishio, J. Chem. Soc., Perkin Trans. 2,
1972, 1730.
21. F. Hammerschmidt, M. Hanbauer, J. Org. Chem., 2000,
65, 6121.
1. D. Michael, P. Mingos, R. H. Crabtree, Comprehensive
Organometallic Chemistry III, Elsevier, Oxford, 2007, Vol. 5.
2. A. G. Ginzburg, Usp. Khim., 2009, 78, 211 [Russ. Chem. Rev.
(Engl. Transl.), 2009, 78].
22. P. Beak, V. Snieckus, Acc. Chem. Res., 1982, 15, 306.
23. M. Tsukazaki, M. Tinkl, A. Roglans, B. J. Chapell, N. J.
Taylor, V. Snieckus, J. Am. Chem. Soc., 1996, 118, 685.
24. Yu. N. Sukharev, V. F. Sizoi, Yu. S. Nekrasov, Org. Mass
Spectrom., 1981, 16, 23.
25. J. Clayden, J. Dufour, D. M. Grainger, M. Helliwell, J. Am.
Chem. Soc., 2007, 129, 7488.
26. S. P. Gubin, K. N. Anisimov, I. P. Shepilov, I. B. Zlotina,
N. E. Kolobova, Izv. Akad. Nauk SSSR, Ser. Khim., 1967,
460 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.),
1967, 16].
27. A. N. Nesmeyanov, K. N. Anisimov, Z. P. Valueva, Dokl.
Akad. Nauk SSSR, 1964, 157, 622 [Dokl. Chem.
(Engl. Transl.), 1964, 157].
28. APEX II Software Package, 2005, Bruker AXS Inc., Madison,
Wisconsin, USA.
29. G. M. Sheldrick, SADABS, 1997, Bruker AXS Inc., Madiꢀ
son, Wisconsin, USA.
30. G. M. Sheldrick, Acta Crystallogr., Sect. A, 2008, 64, 112.
3. N. M. Loim, P. V. Kondratev, N. P. Soloveva, V. A. Anꢀ
tonovich, P. V. Petrovskii, Z. N. Parnes, D. N. Kursanov,
J. Organomet. Chem., 1981, 209, 233.
4. N. M. Loim, M.A. Kondratenko, V. I. Sokolov, Metalloorg.
Khim., 1991, 4, 813 [Organomet. Chem. USSR (Engl. Trans.),
1991, 4, 395].
5. N. M. Loim, M. A. Kondratenko, V. I. Sokolov, J. Org.
Chem., 1994, 59, 7485.
6. N. M. Loim, N. A. Abramova, Z. N. Parnes, D. N. Kurꢀ
sanov, J. Organomet. Chem., 1979, 168, 35.
7. D. N. Kursanov, N. M. Loim, M. V. Larukova, Z. F.
Mullakhmetova, Z. N. Parnes, Dokl. Akad. Nauk SSSR, 1984,
277, 878 [Dokl. Chem. (Engl. Transl.), 1984, 277].
8. R. G. Sutherland, A. K. V. Unni, J. Chem. Soc., Perkin Trans.
2, 1977, 703.
9. N. M. Loim, M. A. Kondratenko, V. I. Sokolov, K. M. Turꢀ
dybekov, Yu. T. Struchkov, Metalloorg. Khim., 1992, 5, 1176
[Organomet. Chem. USSR (Engl. Transl.), 1992, 5, 575].
10. N. M. Loim, M. A. Kondratenko, V. I. Sokolov, Russ. Chem.
Bull. (Engl. Transl.), 1993, 42, 166 [Izv. Akad. Nauk, Ser.
Khim., 1993, 182].
11. S. Kudis, G. Helmchen, Angew. Chem., Int. Ed., 1998,
37, 3047.
Received July 3, 2012;
in revised form October 23, 2012