Rhodium-Catalyzed Highly Regio- and Enantioselective Hydrogenation of Tetrasubstituted Allenyl Sulfones: An Efficient Access to Chiral Allylic Sulfones

Article abstract of DOI:10.1002/anie.201804891

A highly regio- and enantioselective hydrogenation of challenging tetrasubstituted allenyl sulfones has been developed, affording chiral allylic sulfones in good yields with excellent regio- and enantioselectivities (up to 99 % yield and 99 % ee). This me

Full text of DOI:10.1002/anie.201804891

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Accepted Article
Title: Rhodium-Catalyzed Highly Regio- and Enantioselective
Hydrogenation of Tetrasubstituted Allenyl Sulfones: An Efficient
Access to Chiral Allylic Sulfones
Authors: Jiao Long, Liyang Shi, Xiong Li, Hui LV, and Xumu Zhang
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10.1002/anie.201804891
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Rhodium-Catalyzed Highly Regio- and Enantioselective
Hydrogenation of Tetrasubstituted Allenyl Sulfones: An Efficient
Access to Chiral Allylic Sulfones
Jiao Long‡a, Liyang Shi‡a, Xiong Lia, Hui Lv*a,c, and Xumu Zhangb*
Abstract: A highly regio- and enantioselective hydrogenation of
challenging tetrasubstituted allenyl sulfones has been achieved,
affording chiral allylic sulfones in good yields with excellent regio- and
enantioselectivities (up to 99% yield and 99% ee). This method
provides an efficient and concise route to chiral allylic sulfones, thus
offering an atom-economic process with a wide range of potential
applications in organic synthesis and medicinal chemistry.
hydrogenation has become a robust and readily accessible route
to chiral compounds.[7] In this context, our group is devoted to
asymmetric hydrogenation of challenging substrates, and
achieved
enantioselective reduction of tetrasubstituted
enamides,[8] conjugated enamides,[9] conjugated ketones,[10]
electron-deficient alkenes[11]. Very recently, we have achieved
asymmetric hydrogenation of -substituted vinyl sulfones, giving
chiral sulfones with high enantioselectivities.[12] Intrigued by this
result, we envision that allenyl sulfones can be regarded as
methylene-substituted vinyl sulfones, the regioselective semi-
reduction of C=C bonds bearing a sulfone group, due to electronic
effect of the sulfone group, may be achieved, affording chiral
allylic sulfones, which are valuable molecules in life science,
medicine, and chemistry.[13] Herein, we report an efficient access
to chiral allyl sulfones via Rh-catalyzed regio- and
enantioselective semireduction of challenging tetra-substituted
allenyl sulfones (Scheme 1b).
Regio- and enantiocontrolled reduction of conjugated
unsaturated bonds is a fundamental but challenging issue in
modern organic synthesis.[1] To this end, great efforts have been
devoted to this issue and some important progress have been
made.[2] However, compared with the great success in the
regioselective asymmetic hydrogenation of various conjugated
alkenes/ketones,[3] the regio- and enantioselective hydro-
genation of allenes is rarely reported despite the fact that the
asymmetric semireduction of allenes provides an efficient access
to chiral allylic compounds. The main reason may lie in that it’s
very difficult to control the chemo-, regio-, and stereoselectivity
simultaneously. Moreover, this transformation might be further
challenged by the typical regioselectivity to affording internal
alkenes[4] and inevitably forming completely reduction products[5].
In 2017, Dong et al reported their pioneer work in asymmetric
semireduction of 1,1-disubstituted allenes via rhodium catalyzed
transfer hydrogenation by using Hantzsch ester as reductant,
giving chiral benzylic motifs (Scheme 1a). [6] Unfortunately, the
substrate scope of this reaction is limited to 1,1-disubstituted
unfunctionalized allenes, while the asymmetric semireduction of
more steric tetrasubsitituted allenes has not been established.
Thus, it’s highly desirable to develop a new method to achieve
regioselective asymmetric hydrogenation of challenging
tetrasubstituted allenes.
Scheme 1. Enantioselective semireduction of allenes.
In the past decades, transition-metal catalyzed asymmetric
We began the initial investigation with the asymmetric
hydrogenation of tetrasubstituted 1,2-allenyl sulfones 1a to
[a]
Key Laboratory of Biomedical Polymers of Ministry of Education &
College of Chemistry and Molecular Sciences, Wuhan University,
Wuhan, Hubei, 430072, P. R. China.
optimize the reaction conditions (Table 1).
A variety of
diphosphine ligands (Figure 1) developed by our group and some
commercial available chiral ligands were examined when the
reaction was carried out in the presence of 1 mol% [Rh(NBD)2]BF4
in dichloromethane (DCM) at room temperature under 20 atm H2.
As shown in Table 1, axially chiral biaryl bisphosphorus ligands
such as (S)-BINAP, (S)-SegPhos, (S)-DTBM-SegPhos exhibited
excellent activity and enantio-selectivity, but relatively low
regioselectivity, only affording desired product 2a with poor to
moderate yield (Table 1, entries 1-3). When P chiral ligands,
E-mail: huilv@whu.edu.cn
[b]
[c]
Department of Chemistry, Southern University of Science and
Technology, Shenzhen, Guangdong, 518055, P. R. China.
E-mail: zhangxm@sustc.edu.cn
Engineering Research Center of Organosilicon Compounds &
Materials, Ministry of Education, College of Chemistry and Molecular
Sciences, Wuhan University, Wuhan, Hubei, 430072, P. R. China.
[‡]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201804891
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was employed, only afford the target product with low yield and
moderate enantioselectivity (Table 1, entry 6). Chiral
bisphosphine-thiourea ligand ZhaoPhos displayed very low
activity and regioselectivity in this reaction, giving 2a with less
than 5% yield albeit with 93% ee (Table 1, entry 7). To our delight,
when (S)-Binapine was employed as ligand, the reaction worked
very smoothly, generating target product 2a with 82% yield and
99% enantioselectivity (Table1, entry 8). Subsequently, the
exploration of various solvents disclosed that DCM is the best
solvent for this reaction (See Supporting Information). When the
reaction was conducted with shorter reaction time or a lower
hydrogen pressure, there was no improvement in the yield and
enantioselectivity (Table 1, entries 9-10).
Table 2. Ligand Screening for Rh-Catalyzed Asymmetric Hydrogenation of
1h.[a]
Figure 1. Structures of the phosphine ligands for hydrogenation of tetra-
substituted 1,2-allenyl sulfones 1.
Entry
Ligand
Conv.
[%][b]
Yield [%][b]
2h 3h + 4h
ee [%][c]
Table 1. Optimization of the reaction conditions.[a]
1
2
(S)- Binapine
(S)-BINAP
>99
>99
>99
>99
56
56
92
89
84
19
0
44
8
-70
94
75
94
-12
-
3
(Rc,Sp)-DuanPhos
(S)-SegPhos
(R,S)-t-Bu-JosiPhos
f-Binaphane
11
16
37
99
13
0
Entry
Ligand
Conv.
[%][b]
Yield [%][b]
ee [%][c]
4
5
2a
3a + 4a
24
6
>99
78
1
2
(S)-BINAP
(S)-SegPhos
>99
>99
>99
>99
>99
43
74
75
27
73
18
33
< 5
82
83
83
-94
-96
-96
18
7
WalPhos
65
27
56
<5
-21
-60
96
32
22
8
ZhaoPhos
27
3
(S)-DTBM-SegPhos
(S,S)-Me-DuPhos
(Rc,Sp)-DuanPhos
(R,S)-t-Bu-JosiPhos
ZhaoPhos
70
9
(S)-DTBM-SegPhos
TaniaPhos
>99
<5
44
0
4
24
10
5
80
49
[a] Unless otherwise noted, all reactions were carried out with
a
6
8
-47
-93
99
Rh(NBD)2BF4/ligand/substrate (0.1 mmol) ratio of 1:1.1:100 in 1 mL solvent at
room temperature under H2 (10 atm) for 2 h. [b] Yield was determined by 1H
NMR analysis. [c] Determined by HPLC analysis using a chiral stationary phase.
7
16
--
8
(S)- Binapine
>99
>99
>99
16
9[d]
10[e]
(S)- Binapine
15
99
However, when aryl group substituted allenylic sulfone 1h
was tested by using 1 mol% Rh/(S)-Binapine complex as catalyst,
the asymmetric semireduction of allenyl sulfone worked very well
but with poor regioselectivity and moderate enantioselectivity.
Therefore, 1h was chosen as a model substrate to optimize the
reaction conditions for the asymmetric semireduction of aryl
substituted allenyl sulfones. A variety of diphosphine ligands were
evaluated (Table 2, entries 1-10), and the results revealed (S)-
BINAP is superior to all other tested, giving chiral allylic sulfone
2h with 92% yield and 94% ee (Table 2, entry 2).
(S)- Binapine
15
99
[a] Unless otherwise noted, all reactions were carried out with
a
Rh(NBD)2BF4/ligand/substrate (0.1 mmol) ratio of 1:1.1:100 in 1 mL DCM at
room temperature under H2 (20 atm) for 3 h. [b] Yield was determined by 1H
NMR analysis. [c] Determined by HPLC analysis using a chiral stationary phase.
[d] Reaction time was 2 hours. [e] Hydrogen pressure was 10 atm.
such as (S,S)-Me-DuPhos, (RC,SP)-DuanPhos were used, both
the yield and enantioselectivity were depressing (Table 1, entries
4-5). When (R,S)-t-Bu-Josiphos, a typical planar chiral ligand,
With the optimal reaction conditions in hand, we set out to
explore the substrate scope of asymmetric semireduction of
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10.1002/anie.201804891
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tetrasubstituted 1,2-allenylic sulfones. Gratifying, this reaction
exhibited good substrate tolerance and gave chiral allylic sulfone
with excellent enantioselectivity. As shown in Scheme 2, when R
is alkyl group, the asymmetric semireduction of tetrasubstituted
1,2-allenyl sulfones proceeded very smoothly in the presence of
1 mol% [Rh(NBD)2]BF4/(S)-Binapine complex, giving desired
products with excellent enantioselectivities (2a-2g). Generally,
linear alkyl substituted allenyl sulfones have better performance
in enantioselectivity but slightly lower regioselectivity compared
with branched-chain substituted allenyl sulfones. When R is aryl
group, no matter the electronic property or the position of
substituent on the benzene ring, all the aryl group substituted
allenyl sulfones tested here can be hydrogenated in high yields
with high regio- and enantioselectivity by using Rh/(S)-BINAP
complex as catalyst (2h-2n). In addition, when the two methyl
group of the tetrasubstituted allenyl sulfones 1 were replaced by
other type of alkyl, this reaction also worked smoothly and
provided the target product with excellent enantioselectivity but
the yield dropped to some extent (2o). The absolute configuration
of the chiral allylic sulfones was unambiguously established to be
R by single-crystal X-ray analysis of 2h.[14]
To demonstrate the potential utilities of the protocol for
synthesis of chiral allylic sulfones, the reactions were carried out
on gram scale. The reaction was conducted in DCM with 10 atm
H2 at room temperature in presence of
1
mol%
[Rh(NBD)2BF4]/(S)-BINAP complex, affording the desired
products 2a, 2d, and 2h in high yields and excellent
enantioselectivities (Scheme 3a). When the catalyst loading was
decreased to 0.1 mol%, the reaction proceeded very well,
affording 2l in 97% yield and 90% ee (Scheme 3b).
Scheme 3. Gram-scale reaction and S/C evaluation.
In summary, we have developed a highly efficient route to
synthesize chiral allylic sulfones in high yield with good
regioselectivity and excellent enantioselectivity (up to 99% yield
and 99% ee) via asymmetric semireduction of allenyl sulfones. To
the best of our knowledge, this protocol provides the first example
to achieve asymmetric semireduction of challenging
tetrasubstituted allenyl sulfones. Further studies on asymmetric
hydrogention of challenging substrates are ongoing in our
laboratory.
[a] Unless otherwise noted, all reactions were carried out with
a
Acknowledgements
Rh(NBD)2BF4/ligand/substrate (0.2 mmol) ratio of 1:1.1:100 in 1 mL DCM at
room temperature under H2 (10 atm) for 2 h. 2a-2b, 2d-2f were catalyzed by
Rh/(S)-Binapine, 2c, 2g-2o were catalyzed by Rh/(S)-BINAP. All yields are
isolated yields. Enantiomeric excess were determined by HPLC analysis using
a chiral stationary phase.
We are grateful for financial support from the National Natural
Science Foundation of China (Grant Nos. 21402145, 21432007),
the Youth Chen-Guang Science and Technology Project of
Wuhan City (2015071704011640), the Natural Science
Foundation of Hubei Province (2018CFB430), the Fundamental
Research Funds for Central Universities (2042017kf0177), the
Scheme 2. Substrate scope. [a]
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Important Sci-Tech Innovative Project of Hubei Province
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Keywords: allylic sulfone• allene• asymmetric hydrogenation •
enantioselectivity • rhodium
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Jiao Long,+a Liyang Shi,+a Xiong Li, Hui
Lva,* and Xumu Zhangb,*
Page No. – Page No.
Rhodium-Catalyzed Highly Regio-
and Enantioselective Hydrogenation
of Tetrasubstituted Allenyl Sulfones:
An Efficient Access to Chiral Allylic
Sulfones
An efficient access to chiral allylic sulfones: Rhdium catalyzed asymmetric semireduction of challenging tetrasubstituted allenyl
sulfones have been achieved, affording chiral allylic sulfones with high yields and high regio- and enantioselectivities. This protocol
provided an efficient access to chiral allylic sulfones and exhibited protential application prospect in organic synthesis.
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