Rhodium-Catalyzed Diastereoselective Cyclization of Allenyl-Sulfonylcarbamates: A Stereodivergent Approach to 1,3-Aminoalcohol Derivatives

Article abstract of DOI:10.1002/anie.201609366

A diastereoselective and stereodivergent rhodium-catalyzed intramolecular coupling of sulfonylcarbamates with terminal allenes is described and it provides selective access to 1,3-aminoalcohol derivatives, scaffolds found in bioactive compounds. The reaction is compatible with a large range of different functional groups, thus furnishing products with high diastereoselectivities and yields. Moreover, multigram scale reactions, as well as the application of suitable product transformations were demonstrated.

Full text of DOI:10.1002/anie.201609366

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201609366
German Edition: DOI: 10.1002/ange.201609366
Allylic Compounds
Rhodium-Catalyzed Diastereoselective Cyclization of Allenyl-
Sulfonylcarbamates: A Stereodivergent Approach to 1,3-Aminoalcohol
Derivatives
Pierre A. Spreider, Alexander M. Haydl, Marc Heinrich, and Bernhard Breit*
Abstract: A diastereoselective and stereodivergent rhodium-
catalyzed intramolecular coupling of sulfonylcarbamates with
terminal allenes is described and it provides selective access to
1,3-aminoalcohol derivatives, scaffolds found in bioactive
compounds. The reaction is compatible with a large range of
different functional groups, thus furnishing products with high
diastereoselectivities and yields. Moreover, multigram scale
reactions, as well as the application of suitable product
transformations were demonstrated.
addition of different heterocycles[5e,f,h,10] or imines[11] to allenes
and alkynes, the formation of new amine motifs was yet to be
investigated. In this respect, we developed the following
reaction to provide a profitable and stereodivergent access to
1,3-aminoalcohols.
The preparation of allylic amines in general has been
tackled numerous times in the past because of the high value
of its allylic double bond in the resulting product.[12] Aza-
Claisen rearrangement reactions[13] represent a very classical
approach to such allylic amines. Furthermore, transition
metal catalyzed reduction of imines,[14] asymmetric addition
of nucleophiles to imines,[15] and redox-neutral iridium-
Since multiple bioactive compounds such as nikkomycin Z
(a chitin synthase inhibitor),[1] negamycin (an antibiotic
against multiple drug-resistant bacteria),[2] and lopinavir (an
anti-HIV agent),[3] possess an 1,3-aminoalcohol motif in their
backbone (Figure 1), the development of new synthetic tools
for a selective approach to the correct stereochemistry is in
high demand in synthetic organic chemistry.[4]
[15e]
À
catalyzed C C bond-forming imine vinylation
represent
À
an alternative form of C N bond formation. The simulta-
neous construction of allylic 1,3-aminoalcohol motifs, in
particular, represents a challenging task and was thus inves-
tigated recently.[16] Recently reported syntheses of 1,3-amino-
alcohol moieties access, in most cases, a certain diastereose-
lectivity, and suffer from either restricted substrate variability
or are accompanied by the generation of stoichiometric
amounts of waste.[17] Hence, we report a diastereoselective
and stereodivergent rhodium-catalyzed intramolecular addi-
tion of toluenesulfonylcarbamate to terminal allenes to access
N-allylated cyclic carbamates selectively.
Initial reactivity assays were conducted by using a phenyl-
substituted tosylcarbamate in the presence of [{Rh(cod)Cl}2]
(2.0 mol%) and DPEphos (5.0 mol%) in DCE at 808C
(Table 1). In the absence of additives, the syn-configured
product was obtained in a promising yield of 38% and an
excellent d.r. value of 94:6 (entry 1). Inspired by former
results of Oble and co-workers,[18a] the yield of the reaction
could be enhanced by the addition of LiCl as a promotor to
the reaction mixture (entry 2).[18b] Next, to further augment
the yield of this reaction, we focused on subjecting different
acidic additives to this catalysis.[19] Among them, PPTS
showed significant reactivity without decreasing the diaste-
reoselectivity (entry 3). In this respect, altering the reaction
conditions by adding both PPTS and LiCl led to the
corresponding syn-configured product in good yield (81%)
and with an excellent d.r. value of 91:9 (entry 4). To our
surprise, when using benzoic (entry 5) or phenyl isobutyric
acid additives (entry 6) a complete inversion of the diaste-
reoselectivity was observed, thus leading to the anti-config-
ured product 1b in 98% yield and a d.r. value of 88:12
(entry 8). With these optimized reaction conditions in hand,
the scope for this process was studied, while considering
a selective approach to both the syn-configured and the
corresponding counterpart anti-configured product (Table 2
and Table 3).
Figure 1. Bioactive compounds possessing a chiral 1,3-aminoalcohol
scaffold.
Recently, our group described several atom-economical
methodologies for the addition[5] of pronucleophiles to
allenes[6] and alkynes,[7] thus representing an alternative to
transition metal catalyzed allylic oxidation[8] and substitu-
tion[9] to obtain branched allylic products. Being active in the
À
development of C N bond-formation reactions, including the
[*] P. A. Spreider, Dr. A. M. Haydl, M. Heinrich, Prof. Dr. B. Breit
Institut fꢀr Organische Chemie, Albert-Ludwigs-Universitꢁt Freiburg
Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
E-mail: bernhard.breit@chemie.uni-freiburg.de
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201609366.
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Table 1: Rhodium-catalyzed diastereoselective and stereodivergent
addition of sulfonylcarbamates to terminal allenes.
Table 3: Scope of the catalytic diastereoselective addition of sulfonyl-
carbamates to terminal allenes to generate anti-configured com-
pounds.[31][a,b]
Entry
R1
Additive
Yield [%][a]
syn/anti[b]
1
2
3
4
Ph
Ph
Ph
Ph
–
38
57
42
81
94:6
85:15
95:5
91:9
LiCl (100 mol%)
PPTS (50 mol%)
LiCl (30 mol%);
PPTS (30 mol%)
PhCO2H (50 mol%)
PhMe2CCO2H (50 mol%)
PhMe2CCO2H (50 mol%)
PhMe2CCO2H (100 mol%)
5
6
7
8
Ph
Ph
C8H17
C8H17
89
93
77
98
15:85
13:87
24:76
12:88
[a] Combined yield of syn- and anti-configured products as determined by
1H NMR spectroscopy. [b] Diastereoselectivity determined by 1H NMR
analysis of the crude reaction mixture. cod=1,5-cycloocctadiene,
DCE=1,2-dichloroethane, DPEPhos=bis[(2-diphenylphosphino)-
phenyl] ether, PPTS=pyridinium p-toluenesulfonate, PhCO2H=benzoic
acid, PhMe2CCO2H=phenyl isobutyric acid, Ts=4-toluenesulfonyl.
Table 2: Scope of the catalytic diastereoselective addition of sulfonyl-
carbamates to terminal allenes to generate syn-configured com-
pounds.[31][a,b]
1
[a] Combined yield. [b] Diastereoselectivity determined by H NMR
analysis of the crude reaction mixture.
A broad range of functional groups was tolerated in the
catalysis and led to the corresponding cyclic carbamates in
good to excellent yields. Several aromatic moieties with
different electronic properties (1–3) were suitable in this
catalysis. The reaction is tolerant of sterics as shown by the
clean reaction of ortho-, meta-, and para-tolyl-substituted
derivatives (4–6). Functional groups such as ethers, thioeth-
ers, a bromide, or a trifluoromethyl group, attached to the
aromatic moiety, were also well tolerated to afford the desired
products (7–10) in good to excellent yields and d.r. values (up
to 97% and up to 95:5). Starting materials bearing different
heterocycles such as a pyridine or thiophene also behaved
well in terms of yield and diastereoselectivity, as well as
aliphatic substituents such as either an ester or a TBS-silyl
ether.
Gratifyingly, even nitrile- or cyclopropyl-substituted sul-
fonylcarbamates were compatible with the reaction condi-
tions (12, 15). At this point, we were glad to observe that all
resulting diastereomers could easily be separated by column
chromatography. In both cases, the relative configurations of
syn- and anti-configured products were determined by NOE
experiments (15a and 1b) and further confirmed by X-ray
diffraction analysis.[19]
1
[a] Combined yield. [b] Diastereoselectivity determined by H NMR
analysis of the crude reaction mixture. TBS=tert-butyldimethylsilyl.
2
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Next, the suitability of this synthetic methodology for
2 kcalmolÀ1 more stable than its syn-diastereomer. This
stereoselective synthesis was further investigated by exposing
the enantiomerically enriched starting material 19, which was
accessible in one or two steps,[19,20] to a multigram scale
catalysis (Scheme 1). We were pleased to observe that no
erosion in the enantioselectivity took place during the
transformation. Notably, at this point the anti-configured
product could be purified by a single recrystallization, thus
demonstrating the practicality of the approach to the
essentially diastereo- and enantiopure aminoalcohols.
difference suggests that the presence of phenyl isobutyric
acid as a cocatalyst enables the reaction to be under
À
thermodynamic control. That is, the C N bond formation
becomes reversible, thus allowing the anti-configured ther-
modynamic product 1b to be formed.[19,21,22] Hence, the
following mechanistic scheme can be proposed. For the syn-
conditions (Scheme 2, left-hand cycle) the role of PPTS may
be the generation of a rhodium-hydride species (B) to initiate
the catalytic cycle.[23] After hydrometallation of the allene the
À
rhodium-allyl species C is formed. In this case the C N bond-
forming event is more an inner-sphere reductive elimination
process, which is irreversible. The presence of a carboxylic
acid instead of PPTS changes the mechanistic scenario. Thus,
from previous mechanistic investigations we know that
carboxylic acids bind as carboxylate ligands to rhodium(III)
centers.[24] Assuming that carboxylate binding occurs also in
this reaction under the anti-conditions the coordination of the
carbamate to the rhodium center would be prohibited (D).
This scenario suggests that the N-nucleophile attack to the
p-allyl rhodium intermediate may occur as an outer-sphere
attack and is based on the experimental data to most likely be
reversible.
Scheme 1. Gram-scale catalysis. Reagents and conditions: a) [{Rh-
(cod)Cl}2] (2.0 mol%), DPEphos (5.0 mol%), PPTS (30 mol%), and
LiCl (30 mol%) in DCE (0.4m) at 808C for 16 h; 80%, 90% ee.
b) [{Rh(cod)Cl}2] (2.0 mol%), DPEphos (5.0 mol%), and PhCMe2CO2H
(100 mol%) in DCE (0.4m) at 808C for 16 h; 82%, 95% ee.
To further highlight the synthetic utility of this catalytic
reaction, assorted transformations of 1b were elaborated
(Scheme 3). On one hand, the olefin moiety could be
functionalized by hydroformylation using our self-assembly
ligand 6-diphenylphosphinopyridone (6-DPPon).[25] More-
over, the double bond was subjected to either olefin meta-
thesis[26] to deliver 22 with a good selectivity (9:1 E:Z), or to
hydrogenation[27] to furnish 24 in excellent yield (99%). On
the other hand, a bifunctional derivatization by either
reducing the carboxylic group to the unprotected alcohol[28]
(21), cleaving the tosyl group under reductive conditions[29] to
the carbamate 23, or even removing both the tosyl and
carbamate groups to give the corresponding 1,3-aminoalcohol
could be demonstrated.[30]
To gain insight into the origin of the stereodivergency of
this catalysis some preliminary experiments were per-
formed.[19] When the syn-configured carbamate 1a was
subjected to the “anti-conditions”, an inversion of the relative
configuration was observed (Scheme 2). Conversely, subject-
ing the anti-configured carbamate 1b to the “syn-conditions”
the d.r. value remained unchanged. DFT calculations (BP86/
def2SVP) showed that the anti-diastereomer is approximately
Scheme 3. Follow-up chemistry of the allylsulfonylcarbamate. a) [{Rh-
(CO)2acac}] (0.5 mol%), 6-DPPon (10 mol%), CO/H2 (1:1, 20 bar),
toluene, 808C, 18 h, 93% (l/b>95:5). b) Grubbs–Hoveyda II
(10 mol%), 1-phenyl-4-butene, DCM, 508C, 14 h, 67% (9:1 E/Z).
c) Pd/C (10 mol%), H2 (1 atm), MeOH, RT, 18 h, 99%. d) LiAlH4,
Et2O, 08C the RT, 1 h, 97%. e) Mg powder, ultrasonification, MeOH/
THF (2.5:1), RT, 3 h, 91%. f) LiOH, EtOH/H2O (2:1), 1008C, 12 h,
94%. acac=acetylacetonate, DCM=dichloromethane, 6-DPPon=
6-diphenylphosphinopyridin-2-(1H)-one, THF=tetrahydrofuran.
Scheme 2. Mechanistic proposal for the diastereoselective cyclization
of allenyl-sulfonylcarbamates.[20]
.
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In summary, we have accomplished a stereodivergent and
highly diastereoselective method to access allyl-carbamates
by using catalytic amounts of a rhodium/DPEphos system. A
broad range of functional groups is tolerated in this reaction,
thus giving access to a variety of substituted 1,3-amino-
alcohols in good to excellent yields along with high diaste-
reoselectivities. Furthermore, we presented synthetic possi-
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or, alternatively, the elaboration of the allylic moiety. Further
investigations on extending this approach to other suitable
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Acknowledgments
This work was supported by the DFG and the Fonds der
Chemischen Industrie (PhD fellowship to P.S.). We thank
Solvias, Umicore, BASF, and Wacker for generous gifts of
chemicals. Dr. Manfred Keller, Dr. Daniel Kratzert, and Felix
Bauer are acknowledged for highly qualified NMR-, X-ray-
analysis, and DFT calculations.
Keywords: alcohols · allenes · allylic compounds · rhodium ·
synthetic methods
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Received: September 23, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Allylic Compounds
P. A. Spreider, A. M. Haydl, M. Heinrich,
B. Breit*
&&&& — &&&&
Rhodium-Catalyzed Diastereoselective
Cyclization of Allenyl-
Sulfonylcarbamates: A Stereodivergent
Approach to 1,3-Aminoalcohol
Derivatives
Either way: The diastereoselective and
stereodivergent rhodium-catalyzed intra-
molecular coupling of sulfonylcarba-
mates with terminal allenes permits the
selective synthesis of N-allylic 1,3-ami-
noalcohol derivatives. The reaction is
compatible with a large range of func-
tional groups and furnishes products with
high diastereoselectivities and yields.
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!