Synthesis of chiral a-substituted a-amino acid and amine derivatives through Ni-catalyzed asymmetric hydrogenation

Article abstract of DOI:10.1039/d0cc01220c

Highly efficient Ni-catalyzed asymmetric hydrogenation of cyclicN-sulfonyl ketimino esters was, for the first time, successfully developed, providing various chiral a-monosubstituted a-amino acid derivatives with excellent results (97-99% yields, 90 to >99% ee). CyclicN-sulfonyl ketimines were also hydrogenated well to afford chiral amine derivatives with 98-99% yields and 97 to >99% ee. The gram-scale asymmetric hydrogenation was performed well with 85% yield and 99% ee using only 0.2 mol% catalyst.

Full text of DOI:10.1039/d0cc01220c

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DOI: 10.1039/D0CC01220C
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Synthesis of Chiral α-Substituted α-Amino Acid and Amine
Derivatives Through Ni-Catalyzed Asymmetric Hydrogenation
Gongyi Liu,† Xianghe Zhang,† Heng Wang,§ Hengjiang Cong,† Xumu Zhang*§,† and Xiu-Qin Dong,*†
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Highly efficient Ni-catalyzed asymmetric hydrogenation of cyclic N-
Transition metal-catalyzed asymmetric hydrogenation of prochiral
sulfonyl ketimino esters was first successfully developed, providing unsaturated compounds is a facile and direct method to access chiral
various chiral α-monosubstituted α-amino acid derivatives with compounds with the advantages of high atom economy and easy
excellent results (97%-99% yields, 90%->99% ee). The cyclic N- manipulation, which is heavily dependent on precious transition
sulfonyl ketimines were also hydrogenated well to afford chiral metals.16 They could suffer from limited resource, high cost and
amine derivatives with 98%-99% yields and 97%->99% ee. The gram- environmental contamination. As an important strategy, the cheap
scale asymmetric hydrogenation was performed well with 85% yield and earth-abundant transition metal catalytic systems were paid
and 99% ee using only 0.2 mol% catalyst. Interestingly, different increasing attention in recent years, which is helpful to the sustainable
nonlinear effects were observed with substrates cyclic N-sulfonyl development. Some pioneering research works of Ni-catalyzed
ketimino ester 1a and ketimine 1m, which disclosed that there may asymmetric hydrogenation of ketones, alkenes, ketimines and
be different nickel catalytic species in these reaction systems.
enamides have been reported by Hamada,17 Chirik,18 Zhou,19 Zhang20
and our group21. Zhang and coworkers successfully realized the
highest catalytic activity for Ni-catalyzed asymmetric hydrogenation
to date.20a Based on the long-standing study in this field, we are
interested in developing efficient method to synthesize chiral α-
monosubstituted α-amino acid derivatives through Ni-catalyzed
asymmetric hydrogenation. The prochiral cyclic N-sulfonyl ketimines
were proven as preferred substrates to construct chiral amine
derivatives, because the -SO2- group can be easily removed through
simple transformation.22 However, they are mainly restricted to
aryl/alkyl substituted cyclic N-sulfonyl ketimines substrates, the cyclic
N-sulfonyl ketimino esters were not investigated. Herein, we
successfully realized the first Ni-catalyzed asymmetric hydrogenation
of cyclic N-sulfonyl ketimino esters with excellent results, and the
cyclic N-sulfonyl ketimines were also hydrogenated well to afford
chiral amine derivatives (97%-99% yields, 90%->99% ee, Scheme 1).
Chiral α-monosubstituted α-amino acid derivatives represent as an
important class of nonproteinogenic amino acid derivatives, which are
universally distributed in many pharmaceuticals and biologically
active molecules.1-6 In addition, they can be served as versatile chiral
building blocks, auxiliaries, ligands in the field of asymmetric
synthesis.7-8 Owing to the enormous importance of chiral α-
substituted α-amino acids and derivatives, they have attracted great
attention in the last decades, and many asymmetric catalytic synthetic
methodologies have been well established.1c-1d, 9-15 However, most of
them were focused on the synthesis of chiral α,α-disubstituted α-
amino acid derivatives,10-15 such as asymmetric addition of organic
boronic reagents or terminal alkynes to ketimino esters,10 allylation12
and alkylation13 of ketimino ester derivatives, addition of β-ketoesters
or α-cyanoacetates to azodicarboxylate esters,14 and 1,3-
cycloaddition of azomethine ylides15. Comparatively, the asymmetric
catalytic reaction types for the synthesis of chiral α-monosubstituted
α-amino acid derivatives were relatively less explored, and it is
necessary to develop new and efficient synthetic methods.
a
Key Laboratory of Biomedical Polymers, Engineering Research Center of
Scheme 1. Ni-catalyzed asymmetric hydrogenation of cyclic N-sulfonyl ketimino esters
and ketimines.
Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry
and Molecular Sciences, Suzhou Institute of Wuhan University, Wuhan University,
Wuhan, Hubei, 430072, P. R. China.
Our preliminary investigation for the Ni-catalyzed asymmetric
hydrogenation of cyclic N-sulfonyl ketimino ester was conducted with
model substrate ethyl benzo[e][1,2,3]oxathiazine-4-carboxylate 2,2-
dioxide 1a under 50 atm H2 in hexafluoroisopropanol (HFIP). As shown
b Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science
and Technology, Shenzhen, Guangdong, 518055, P. R. China.
E-mail address: zhangxm@sustc.edu.cn, xiuqindong@whu.edu.cn.
‡ Electronic supplementary information (ESI) available: Experimental procedures, NMR
spectra of compounds. See DOI: 10.1039/x0xx00000x.
This journal is © The Royal Society of Chemistry 20xx
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Table 2. Screening solvents for Ni-catalyzed asymmetric hydrogenation of 1a. a
in Table 1, a variety of chiral diphosphine ligands were applied. Full
conversion and moderate enantioselectivity was provided with
(Rc,Sp)-DuanPhos as the ligand (>99% conversion, 64% ee, Table 1,
entry 1). Poor reactivities and enantioselectivities were observed in
the presence of (S)-Binapine, (S,S)-Me-DuPhos (6%-13% conversions,
30% ee, Table 1, entries 2, 5). There was trace conversion or no
reaction using ligands (S)-BINAP, ZhaoPhos, (S)-SegPhos and WalPhos
(Table 1, entries 4, 6-8). To our delight, the (S,S)-Ph-BPE gave full
conversion and 96% ee (Table 1, entry 3).
View Article Online
DOI: 10.1039/D0CC01220C
Entry
Solvent
Conv. (%)b
Ee (%)c
1
2
3
4
5
6
7
8
HFIP
TFE
>99
97
10
NR
NR
90
7
96
96
96
NA
NA
96
30
NA
MeOH
iPrOH
Table 1. Screening ligands for Ni-catalyzed asymmetric hydrogenation of 1a. a
1,4-dioxane
CH2Cl2
toluene
THF
Entry
Ligand
Conv. (%)b
Ee (%)c
NR
1
2
3
4
5
6
7
8
(Rc,Sp)-DuanPhos
(S)-Binapine
(S,S)-Ph-BPE
(S)-BINAP
>99
13
64
30
96
70
30
NA
33
NA
a
Unless otherwise noted, all reactions were carried out with a Ni(OAc)2/(S,S)-Ph-
BPE/1a (0.05 mmol) ratio of 1:1.1:50 at 50 oC in 0.7 mL solvent under 50 atm H2 for
2 h. b Determined by 1H NMR analysis. c Determined by HPLC on a chiral phase.
>99
trace
6
investigate the substrate scope. These results were summarized
in Scheme 2. The cyclic N-sulfonyl ketimino ethyl esters
(S,S)-Me-DuPhos
ZhaoPhos
NR
containing electron-donating (1b
1g 1h) substituents on the benzo ring were hydrogenated well
to give the products (2b 2h 2j) with 97%-99% yields and
-1f, 1j) or electron-withdrawing
(
-
(S)-SegPhos
WalPhos
trace
NR
-
,
90%->99% ee. The naphthalene-fused ketimino ethyl ester 1i
also worked efficiently with 98% yield and 94% ee. Further
investigation on the ester group indicated that there is almost no
effect on the reactivity and enantioselectivity of the substrates
a
Unless otherwise noted, all reactions were carried out with a Ni(OAc)2/ligand/1a
(0.05 mmol) ratio of 1:1.1:50 at 50 oC in 0.7 mL HFIP under 50 atm H2 for 2 h.
Determined by 1H NMR analysis. c Determined by HPLC on a chiral phase. NR = No
Reation, NA = Not Available.
b
Scheme 2. Substrate scope study for Ni-catalyzed asymmetric hydrogenation of cyclic N-
sulfonyl α-ketimino esters. a
Figure 1. The structures of chiral bisphosphine ligands.
The solvent effect was then inspected for this Ni(OAc)2/(S,S)-Ph-
BPE-catalyzed asymmetric hydrogenation of model substrate 1a. High
conversions and excellent enantioselectivities were obtained in HFIP,
TFE (trifluoroethanol) and CH2Cl2 (90%->99% conversions, 96% ee,
Table 2, entries 1-2, 6). Although 96% ee was provided in MeOH, poor
conversion was detected (Table 2, entry 3). This hydrogenation did
i
not proceed in PrOH, 1,4-dioxane, THF (tetrahydrofuran) (Table 2,
entries 4-5, 8). Poor reactivity and enantioselectivity was afforded in
toluene (7% conversion, 30% ee, Table 2, entry 7). Therefore, HFIP
was found as the best solvent for this Ni-catalyzed hydrogenation.
Once the optimized reaction conditions were established, a wide
range of cyclic N-sulfonyl ketimino esters were inspected to
2 | J. Name., 2012, 00, 1-3
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a
Unless otherwise noted, all reactions were carried out with a Ni(OAc)2/(S,S)-Ph-
Scheme 4. Asymmetric hydrogenation of five-membered ketimino ester 1t, ketimine 1m
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BPE/substrate 1 (0.05 mmol) ratio of 1:1.1:50 at 50 oC in 0.7 mL HFIP under 50 atm H2 for
2 h. Conversion was determined by 1H NMR analysis. The yield was isolated yield. Ee was
determined by HPLC on a chiral phase. b S/C = 50, 3 h. c S/C = 20, 4 h.
and transformation.
DOI: 10.1039/D0CC01220C
with different ester groups. The substrates with methyl ester
group 1k or isopropyl ester group 1l were hydrogenated well,
affording products 2k-2l with 99% yield and 97% ee.
Encouraged by the above excellent performance of this
catalytic system, we began to explore other cyclic N-sulfonyl
ketimines for further substrate scope study. By varying the ester
group to alkyl or aryl group, a series of cyclic N-sulfonyl ketimines
were evaluated (Scheme 3). When the ester group was replaced
by methyl, ethyl and n-propyl group, the expected products 2m
2o were afforded with 98%-99% yields and 98%->99% ee. The
substrates (1p 1r) bearing substituted group on the benzo ring
-
-
with diverse electronic properties and positions were employed
well. Moreover, when the alkyl group was changed to phenyl
group, the substrate 1s was applied to obtain product 2s with 98%
yield and 98% ee.23a
initial chiral species.24 However, linear effect was discovered in the
reduction of substrate cyclic N-sulfonyl ketamine 1m (Figure 2, right),
which disclosed that there should be no catalyst self-aggregation or
ligand-substrate agglomeration in this catalytic system.24 These
results exhibited that it is possible to have different catalytic species
in the hydrogenation of these two kinds of substrates.
Scheme 3. Substrate scope study for Ni-catalyzed asymmetric hydrogenation of cyclic N-
sulfonyl ketimines.a
Figure 2. Ni-catalyzed hydrogenation of substrate 1a (left) and 1m (right) using ligand
(S,S)-Ph-BPE with different ee values.
In summary, we developed an efficient Ni-catalyzed asymmetric
hydrogenation of cyclic N-sulfonyl ketimino esters and cyclic N-
sulfonyl ketimines to prepare a series of chiral α-monosubstituted α-
amino acid derivatives and chiral amine derivatives with excellent
results (97%-99% yields, 90%->99% ee). Additionally, this asymmetric
hydrogenation was performed well on gram-scale without loss of
enantioselectivity. Different nonlinear effects were observed with
these substrates, which disclosed that there may be different nickel
catalytic species in these reaction systems.
We are grateful for financial support from the Natural Science
Foundation of Jiangsu Province (Grant No. BK20190213), Wuhan
Morning Light Plan of Youth Science and Technology (Grant No.
2017050304010307), Shenzhen Science and Technology Innovation
Committee (Grant No. KQTD20150717103157174).
a
Unless otherwise noted, all reactions were carried out with a Ni(OAc)2/(S,S)-Ph-
BPE/substrate 1 (0.05 mmol) ratio of 1:1.1:50 at 50 oC in 0.7 mL HFIP under 50 atm H2 for
2 h. Conversion was determined by 1H NMR analysis. The yield was isolated yield. Ee was
determined by HPLC on a chiral phase.
To our delight, the five-membered cyclic N-sulfonyl ketimino ester
1t was also hydrogenated well to obtain product 2t with 97%
conversion and 95% ee within 0.5 h (Scheme 4a), the corresponding
acid derivative may be used as a chiral auxiliary in asymmetric
synthesis.7 Moreover, the gram-scale asymmetric hydrogenation of
substrate 1m was proceeded efficiently with only 0.2 mol% catalyst,
affording product 2m with 88% conversion, 85% yield and 99% ee
(Scheme 4b). To demonstrate the utility of this methodology, the
hydrogenation product 2b was reduced by LiAlH4 to cyclic N-sulfonyl
amino alcohol 3 in 83% yield with little erosion of ee value (92% ee) at
room temperature, which can be improved to >99% ee through
simple recrystallization in CH2Cl2 and hexane (Scheme 4c).23b
Subsequently, the nonlinear effect experiments were conducted,
a series of Ni-catalyzed asymmetric hydrogenation of model substrate
1a were conducted in the presence of the (S,S)-Ph-BPE ligand with
varying enantiopurity. As shown in Figure 2 left, a positive nonlinear
effect was observed, which may arise the auto association of these
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4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC01220C
Ph
O
O
O
O
Ph
S
S
O
NH
R'
O
N
Ni(OAc)2/(S,S)-PhBPE
H2
P
P
R'
R
R
Ph Ph
(S,S)-Ph-BPE
R' = ester, alkyl, aryl group
97%-99% yield
90%->99% ee
cheap transition metal Ni-catalyzed system
high reactivity and excellent enantioselectivity
wide substrate scope
gram-scale synthesis
Efficient Ni-catalyzed asymmetric hydrogenation of cyclic N-sulfonyl ketimino esters and ketimines
was successfully developed to prepare a series of chiral α-monosubstituted α-amino acid
derivatives and chiral amine derivatives with excellent results (97%-99% yields, 90%->99% ee).