Construction of All-Carbon Chiral Quaternary Centers through CuI-Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1-Disubstituted Allenes with CO2

Article abstract of DOI:10.1002/chem.201903906

A catalytic enantioselective construction of all-carbon chiral quaternary centers through reductive hydroxymethylation of 1,1-disubstituted allenes with CO₂ has been developed. In the presence of a copper/Mandyphos catalyst, CO₂ is t

Full text of DOI:10.1002/chem.201903906

A Journal of
Accepted Article
Title: Construction of All-Carbon Chiral Quaternary Centers via Cu(I)-
Catalyzed Enantioselective Reductive Hydroxymethylation of 1,
1-Disubstituted Allenes with CO2
Authors: Kuiling Ding, Jia Qiu, Shen Gao, Chaopeng Li, Lei Zhang,
Zheng Wang, and Xiaoming Wang
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To be cited as: Chem. Eur. J. 10.1002/chem.201903906
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COMMUNICATION
Construction of All-Carbon Chiral Quaternary Centers via Cu(I)-
Catalyzed Enantioselective Reductive Hydroxymethylation of 1, 1-
Disubstituted Allenes with CO2
*
Jia Qiu,ab Shen Gao,ab Chaopeng Li,ab Lei Zhang,a Zheng Wang,a* Xiaoming Wanga and Kuiling Dingabc
Dedication ((optional))
Abstract: A catalytic enantioselective construction of all-carbon chiral
quaternary centers via reductive hydroxymethylation of 1, 1-
disubstituted allenes with CO2 has been developed. In the presence
of a copper/Mandyphos catalyst, CO2 is transformed into an alcohol
oxidation level via an asymmetric reductive C-C bond formation with
allenes using hydrosilane (HSi(OMe)2Me) as a reductant. The
resulting chiral homoallylic alcohols are versatile synthetic
intermediates and can be conveniently converted into a variety of
useful chiral chemicals.
good enantioselectivities (71:29 to 83:17 er).[6] Therefore, the
development of novel methodology for catalytic enantioselective
construction of all-carbon chiral quaternary centers[7] using CO2 is
highly demanding. The challenging issues associated with the
above-mentioned CO2 transformation include inherent kinetic
inertness of CO2 because of its thermodynamic stablility and the
difficulty for control of enantioselectivity due to the bulky steric
hindrance of quaternary carbon center in the product. We
envisoned that the reaction between a γ,γ-disubstituted allyl metal
intermediate and CO2 via a transition state of six-membered ring
would be feasible for the formation of the chiral quaternary carbon
center since the new C-C bond formation prefers the more
hindered site of the allylic structure.[8] Herein in this
As an abundant, nontoxic and sustainable carbon feedstock, CO2
attracts much attention from synthetic communities.[1] Over the
past several decades, although extensive efforts have been
devoted to the CO2 incorporation onto high value-added organic
chemicals,[2] asymmetric catalytic reactions using CO2 to form
enantioenriched molecules still remains a nontrivial challenge.[3]
In 2004, Mori and coworkers pionneered a nickel-catalyzed
asymmetric carboxylative cyclization of bis-1,3-dienes (Scheme
1a).[4] More recently, Yu et. al. reported a copper-catalyzed
enantioselective reductive hydroxymethylation of styrene/1,3-
dienes and CO2 (Scheme 1b).[5] Both reactions can be carried out
under mild conditions, and the yields and enantioselectivities are
generally high for construction of chiral tertiary carbon centers.
However, enantioselective formation of chiral all-carbon
quaternary centers using CO2 has been rarely explored. The only
example for the incroproation of CO2 into the construction of
molecules with quaternary carbon stereocenters was reported by
communication,
a
Cu catalyzed asymmetric reductive
hydroxymethylation of 1,1-disubstituted allenes with CO2 in the
presence of hydrosilane as a reductant will be reported, to furnish
an array of homoallylic alcohols bearing a chiral quaternary
carbon center in high yields and good to excellent
enantioselectivities (Scheme 1d).
Mikami in 2016 through
a
Rh-catalyzed asymmetric
hydrocarboxylation of α,β-unsaturated esters (Scheme 1c) in the
presence of stoichiometric amount of diethylzinc with moderate to
[a] J. Qiu, S. Gao, C. Li, Dr. L. Zhang, Prof. Dr. Z. Wang, Dr X. Wang,
Prof. Dr. K. Ding, State Key Laboratory of Organometallic
Chemistry, Center for Excellence in Molecular Synthesis, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences 345
Lingling Road, Shanghai 200032 (China)
Fax: Int. code + (21)-6416-6128
E-mail: wzsioc@mail.sioc.ac.cn
Scheme 1. Enantioselective construction of chiral centers involving C-C bond
formation with CO2
kding@mail.sioc.ac.cn
[b] J. Qiu, S. Gao, C. Li, Prof. Dr. K. Ding
University of Chinese Academy of Sciences, Beijing 100049 (China)
[c] Prof. Dr. K. Ding
Hydroxymethyl (-CH2OH) represents a useful functional moiety
that often exists in natural products and drugs.[9] Introducing
hydroxymethyl into an organic molecule can result in a change of
physical properties including polarity and lipophilicity, which may
significantly modify the biological activity of the compound.[10] In
this respect, Tsuji and co-workers have reported the synthesis of
homoallylic alcohols via Cu(I)-catalyzed hydroxymethylation of
Collaborative Innovation Center of Chemical Science and
Engineering, Nankai University, Tianjin 300071 (China)
Supporting information for this article is given via a link at the end of
the document.
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1,1-disubstituted allenes[11] with CO2 in the presence of
HSi(OMe)2Me.[2q] Good reactivity and regioslectivity were
disclosed with Cu-xyl-Xantphos catalyst system. However, there
has been no any example of an enantioselective version being
reported for construction of β-quaternary homoallylic alcohols
using CO2, to the best of our knowledge.
3). With L4 as the ligand, simlar results were obtained(entries 4).
Among the Phanephos-type ligands L5-L7 (entries 5-7), L6
results in the best results in terms of both yield and
enantioselectivity, affording 2a in nearly quantitative yield (99%)
with good enantioselectivity (85:15 er, entry 6). Several ferrocene-
based chiral diphosphines of the Mandyphos family have also
been examined, and a remarkable yet subtle substituent effect of
the ligand on the catalysis was observed. Whereas with L8, the
prototype Ph-substituted Mandyphos ligand, the reaction gave 2a
with only moderate er (31:69, entry 8), the reaction with L9
bearing larger and more electron donating substituents (3,5-di-
Me-C6H3) on the PAr2 moieties of the Mandyphos-type ligand
gave 2a with a drastically improved er value (90:10 er, entry 9).
However, with L10, bearing a sterically similar but electron
withdrawing 3,5-di-CF3-C6H3 groups on the Mandyphos as the
ligand, only trace amount of 2a was detected under otherwise
identical reaction conditions (entry 10). Intriguingly, for the
reaction mediated by L11, a Mandyphos ligand with cyclohexyl
(Cy) groups on the phosphorous atoms, only modest yield of 2a
(21%) was obtained with a low er (38:62, entry 11). For the
reaction with L12, the Mandyphos ligand bearing 3,5-di-Me-4-
OMeC6H2 groups on its P donors, 2a was obtained with good er
(12:88, entry 12) albeit in low yield. Overall, Mmandyphos ligand
L9 turned out to be optimal in terms of reactivity and stereocontrol,
to produce 2a in good yield (80%) and high enantioselectivity
(90:10 er, entry 9). Subsequently, several common solvents were
screened (see SI for details) and trans-decaline turns out to be
optimal, affording 2a in 99% yield with 91:9 er ratio (entry 13). The
enantioselectivity could be futher improved to 93:7 er when the
temperature was decreased to -20 °C (entry 14). Finally,
evaluation of additives uncovered that 2, 2, 2-trifluoroethanol
(TFE) exhibited a slightly beneficial effect on the catalysis to give
2a in 88% isolated yield and 95:5 er (entry 15), probably as a
result of rapid quenching of the intermediate to facilitate CuH
regeneration and a more organized transition state structure by
H-bonding interaction.[13]
Table 1. Optimization of conditions for the reductive hydroxymethylation of 1,1-
[a]
disubstituted allene 1a with CO2
Entry
Ligand
L1
Yield/%[b]
33
er[c]
70:30
82:18
77:23
23:77
38:62
85:15
30:70
31:69
90:10
-
1
2
3
L2
43
L3
55
4
L4
42
5
L5
45
6
L6
99
7
L7
23
8
L8
71
9
L9
80
10
11
12
13[d]
14[d,e]
15[d,e,f]
L10
L11
L12
L9
trace
21
38:62
12:88
91:9
Under the optimized reaction conditions, the substrate scope of
the allenes were then examined (Table 2). For the reaction of
model substrate 1a, the corresponding product 2a was obtained
in good yield and excellent enantioselectivity even the reaction
was scaled up to gram scale. 1,1-Disubstituted allenes bearing
either electron-donating (1b and 1c) or electron-withdrawing
groups (1d-g) on the para-position of phenyl ring were well
tolerated, affording the corresponding homoallylic alcohols 2b-h
in moderate to good yields and high enantioselectivities. Similar
results were obtained for the reactions of allenes with meta-
substituent (Me or Cl) on the phenyl ring (1i and 1j). For reaction
of substrate 1k with an ortho-tolyl moiety, the corresponding
product 2k was obtained in excellent yield (93%) albeit with a
moderate er value (87:13). Similarly, the reaction of allene 1l
having an ortho-F on the phenyl group afforded
30
99
L9
90
93:7
L9
92(88)[g]
95:5
[a] Unless otherwise stated, the reaction was carried out with 1a (0.5 mmol),
CuOAc (0.015 mmol), HSi(OMe)2Me (4.0 mmol) and the specified ligand (0.015
mmol) in 5 mL of CyH for 20 h under 1 atm of CO2. [b] The yield of 2a was
determined by GC analysis using hexadecane as an internal standard. [c] The
enantiomeric ratio (er) was determined by HPLC on a chiral ID-3 column. [d]
trans-Decaline was used instead of CyH as solvent. [e] -20 °C. [f] 1.5 equiv. TFE
added. [g] Yield of the isolated product. CyH = cyclohexane. TFE = 2,2,2-
trifluoroethanol.
The inverstigation was initiated using 1-phenyl-1-methyl-allene
(1a) as a model substrate under ambient pressure of CO2 with
HSi(OMe)2Me as the reductant in the presence of Cu(I)
complexes of a chiral diphosphane as catalysts (Table 1). SKP
l,[12] a chiral bisphosphine ligand developed by our group, was first
applied to the reaction. Unfortunately, at 10 °C only moderate
reactivity and modest enantioselectivity (was found for Cu(I)/SKP
in the reaction 33% yield with 70:30 er, entry 1). Under otherwise
identical conditions, other chiral bisphosphine ligands were then
tested to enhance the reactivity and enantioselectivity of the
transformation. With Segphos-type ligands L2 or L3, 2a was
afforded with good er values but in moderate yields (entries 2 and
Table 2. Substrate scope for the reductive hydroxymethylation of 1a-1s [a]
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chiral drug (S)-atromepine 3.[14a] The synthetic utilities of the
methodology were further exemplified in several transformations
of 2a (Scheme 2). Selective oxidation of the hydroxyl group in 2a
with Dess-Martin periodinane afforded α-chiral quaternary
aldehyde 4 in high yield, which can be ultilized for various C-C, C-
N, and C-S bond forming reactions.[15] Hydroboration of the C=C
double bond in 2a and peroxide oxidation gave an 88% yield of
diol 5. Mercury trifluoroacetate mediated enylation of hydroxyl
group in 2a followed by an intramolecular RCM reaction with
Grubbs second-generation catalyst afforded a dihydrofuran
derivate
6
in good yield. Finally,
a
Pd-catalyzed
hydrocarbonylation and intramolecular alkoxylation furnished δ-
lactone 7 in high yield with excellent regioselectivity.
Scheme 2 Product transformations and synthetic utility of 2a.
Two control experiments were carried out to shed some light on
the mechanism of this reaction (Figure 1a,b, see SI for more
details). Although hydrosilylation of CO2 proceeds smoothly even
at -20 °C via copper catalysis to give silyl formate 8 in the absence
of allene substrate 1 (Figure 1a), no product 2a was detected
when the isolated silyl formate 8 was submitted to the reaction
with allene 1a under standard conditions except without CO2
(Figure 1b), indicating that silyl formate 8 is not an viable
intermediate for producing homoallylic alcohol. The requirement
for a large excess of silane in this transformation could be
accordingly explained by this competitive but unproductive
transformation. Based on the results mentioned above and
previous studies of literature,[2q,5,8] a plausible mechanism is
outlined in Figure 1c. Treatment of the catalyst precursor with
hydrosilane may lead to the generation of copper hydride species
I through a σ-bond metathesis.[16] Insertion of the allene 1 into the
Cu-H bond of I would result in preferential formation of allylcopper
intermediate II, wherein the bulky Cu-Mandyphos moietymight
locate at the less hindered unsubstited terminal site to minimize
steric congestion. The allylcopper intermediate II can undergo
further reaction with CO2 at its prochiral γ-position via a six-
membered ring transition state,[8] thus leading to enantioselective
and regioselective formation of the key C-C bond in copper
carboxylate III. Further reduction of the resultant III by hydrosilane
finally would give the copper alkoxide IV, which can undergo σ-
bond metathesis with hydrosilane to provide silyl ether V and
regenerate the copper hydride species I. The protic workup of silyl
ether V can finally release the homoallylic alcohol product 2.
[a] Unless otherwise specified, the reaction was generally carried out with the
allene (0.5 mmol), HSi(OMe)2Me (4.0 mmol), CuOAc (0.015 mmol), L8 (0.015
mmol) and TFE (0.75 mmol) in 5 mL trans-decaline for 20 h at -20 °C under 1
atm of CO2. Yields are of the isolated products, and er values were determined
by HPLC on a chiral stationary phase. The absolute configurations of 2a-c, 2e-
h, 2o, 2s-v were determined to be R by comparison of the optical rotations with
literature reported values[14], and those of 2d, 2i, 2k-n, 2p and2r were assigned
to be R and 2q to be S on the basis of their Cotton effect in circular dichroism
(CD) spectra. [b] 8 mmol of 1a, 1.04 g. [c] THF:trans-Decaline (1:1, 5 mL) was
used as solvent.
homoallylic alcohol 2l in 86% yield with 80:20 er. Substrates 1m-
p bearing two or three substituents on phenyl groups were also
amenable to the protocol, affording corresponding products 2k-n
in good yields (81-89%) with high er values (81:19-91:9). The
identity of R1 was found to have a substantial impact on the
enantioselectivity. For example, the reaction of 1q with an ethyl
group gave rise to 2q in excellent yield (90%) but with slightly
decreased er value (86:14) as compared to that of 2a. On the
other hand, the reaction of the allene 1r with
a
tetrahydronaphthalenyl substituent furnished corresponding
product 2r in good yield (81%) with excellent enantioselectivity
(95:5 er). 1, 1-Disubstituted allenes 1s and 1t bearing thiophenyl
and naphthalenyl moiety, respectively, were also examined in the
reaction, affording the products 2s and 2t, in moderate to good
yields with high er values (90:10-93:7). Finally, the reaction of 1,
1-dialkyl substituted allene 1u and 1v also proceeded smoothly to
give 2s and 2v in high yield (93% and 90%) and good to medium
er value (83:17 and 63: 37).
Chiral homoallylic alcohols 2 can be used as versatile
intermediates for synthetic elaboration to various chemicals. In
fact, 2a has been used as a key intermediate in the synthesis of
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Figure 1. Control experiments (a,b) and proposed mechanism (c)
In summary, we have developed a Cu(I)/diphosphine catalyzed
asymmetric reductive hydroxymethylation of 1, 1-disubstituted
allenes with CO2 and hydrosilane, affording a variety of chiral
homoallylic alcohols bearing an all-carbon quaternary chiral
center in high yields and good enantioselectivities. Synthetic
utilities of the protocol were demonstrated in several
transformations of the product 2a. Overall, we hope this
application of CO2 in the construction of quaternary chiral center
would stimulate further development of catalytic asymmetric
catalysis using CO2 as a C1 component in organic synthesis.
Acknowledgements
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[6] S. Kawashima, K. Aikawa, K. Mikami, Eur. J. Org. Chem. 2016, 3166.
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L. E. Overman, Nature 2014, 516, 181.
We thank the financial support from Ministry of Science and
Technology of China (2016YFA0202900), the National Natural
Science Foundation of China (21572254, 21790333, 21772221),
and CAS (XDB20000000, QYZDY-SSW-SLH012).
Keywords: CO2 transformation · quaternary center · allene ·
copper · asymmetric catalysis
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Construction of All-Carbon Chiral
Quaternary Centers via Cu(I)-
catalyzed Enantioselective Reductive
Hydroxymethylation of 1,1-
CO2 for construction of chiral quaternary center:
CO2 has been
enantioselectively engaged in an all-cabon quaternary center construction via a
Cu(I)-catalyzed enantioselective reductive hydroxymethylation of 1,1-disubstituted
allenes in the presence of Mandyphos as a chiral ligand and hydrosilane as a
reductant.
Disubstituted Allenes with CO2
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