Chiral Aluminum Complex Controls Enantioselective Nickel-Catalyzed Synthesis of Indenes: C?CN Bond Activation

Article abstract of DOI:10.1002/anie.202001142

A chiral aluminum complex controlled, enantioselective nickel-catalyzed domino reaction of aryl nitriles and alkynes proceeding by C?CN bond activation was developed. The reaction provides various indenes, bearing chiral all-carbon quaternary centers, under mild reaction conditions in yields of 32 to 91 percent and ee values within the 73–98 percent range. The reaction mechanism and aspects of stereocontrol were investigated by DFT calculations.

Full text of DOI:10.1002/anie.202001142

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Accepted Article
Title: Chiral Aluminum-Controlled Ni-catalyzed Enantioselective
Synthesis of Indenes via C−CN Bond Activation
Authors: Tao Zhang, Yu-Xin Luan, su-Juan zheng, qian peng, and
Mengchun Ye
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202001142
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10.1002/anie.202001142
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Chiral Aluminum-Controlled Ni-catalyzed Enantioselective
Synthesis of Indenes via CCN Bond Activation
Tao Zhang, Yu-Xin Luan, Su-Juan Zheng, Qian Peng*, Mengchun Ye*
Abstract:
A
chiral aluminum-controlled enantioselective Ni-
This process not only eliminated the requirement of directing
groups and additional oxidants in the CH domino reaction, but
also allowed the formation of three CC bonds in one step with
complete atom economy, affording versatile alkyl nitrile-
containing indenes.
catalyzed domino reaction of aryl nitriles and alkynes via CCN bond
activation was developed, providing various indenes bearing chiral
all-carbon quaternary centers in 3291% yield and 7398% ee under
very mild conditions. The reaction mechanism and rational stereo-
control were proposed by DFT calculations.
Indenes bearing all-carbon quaternary stereocenters are
important structural motifs that are frequently found in bioactive
molecules and organic materials.[1,2] Many racemic synthetic
methods have been developed to prepare them,[3] while
enantioselective versions are quite scarce because the rigid ring
and the sterically-hindered carbon center renders asymmetric
control pretty challenging. Typical intermolecular asymmetric
methods are direct functionalization of indene ring (Scheme 1a,
path a),[4] including butyl lithium-mediated SN2 reaction,[5]
organocatalyst-promoted [4+2] and [2+1] cyclization[6] and chiral
phosphine-enabled allylic alkylation.[7] However, given relatively
difficult preparation of indene rings, ring construction via
transition metal-catalyzed domino process seems to be more
efficient because this protocol can assemble arenes and alkynes
into indene rings and quaternary carbon centers concurrently
(path b). Although similar asymmetric domino reactions for
synthesis of indenes bearing non-all-carbon quaternary center
have been reported,[8] constructing chiral all-carbon quaternary
center has been a big challenge. It was until 2015,[9] when Luan
and coworkers reported an enantioselective Pd-catalyzed
dearomatization reaction by using CBr bond as a domino
starting point, affording a series of spiroindenes in up to 97% ee
(Scheme 1b, eq (1)). Almost at the same time, You group used
aryl CH bond instead of CBr bond as a domino starting point
to achieve a similar dearomatized route to various spiroindenes
in up to 94% ee (eq (2)).[10] In the same year, Lam group also
reported a domino process to a series of spiroindenes in up to
97% ee (eq (3)), in which aryl CH bond was still used as the
starting point, but an enolate trapping step was devised to
replace the dearomization step.[11] Despite these elegant works,
the synthesis of easy-to-modified indenes bearing all-carbon
quaternary stereocenters from readily available arenes is still in
high demand. Herein, we report a new domino process that uses
CC bond as a starting point for the first time to prepare chiral
non-spiro indenes in 3291% yield and up to 98% ee (eq (4)).[12]
Scheme 1. Enantioselective intermolecular reaction for syntheses of indenes
bearing all-carbon quaternary stereocenters.
Carbocyanations of -unsaturated compounds such as
alkynes,[13] dienes,[14] and alkenes[15,16] through transition metal-
catalyzed CCN bond activation have been widely explored,[17]
and the use of Lewis acids as co-catalysts and phosphines as
ligands proved critical to the reaction efficiency. And thus, aryl
nitrile 1a and oct-4-yne (2a) were selected as model substrates
and subjected to a broad range of phosphine ligands and Lewis
acids first (Scheme 2a). When PPh3 was used as the ligand,
AlMe2Cl proved to be the optimal one among various screened
Lewis acids (entries 16), providing the desired domino cyclized
product 3a in 80% yield (entry 5). Subsequently, with AlMe2Cl as
the Lewis acid, different phosphine ligands were examined and
[*]
T. Zhang, Y.-X. Luan, S.-J Zheng, Q. Peng, M. Ye
State Key Laboratory and Institute of Elemento-Organic Chemistry,
College of Chemistry, Nankai University, Tianjin 300071 (China)
E-mail: mcye@nankai.edu.cn; qpeng@nankai.edu.cn
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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showed a big influence on the reactivity (entries 710). Ph2PMe
gave the best yield (96%, entry 7), whereas both trialkyl
phosphine (entry 9) and bisphosphine (entry 10) significantly
retarded the reaction. With this optimal racemic conditions in
hand, we explored several strategies for asymmetric control
(Scheme 2b, A to C). However, disappointedly, either low yields
or low ees were obtained in all cases (see the Supporting
Information, Table S4). We reasoned that low ee of mono
phosphines could be attributed into free rotation of NiP bond
(A), and low reactivity of bidendate phosphines could result from
saturated coordination of nickel, which hindered alkenes from
approaching to the catalyst (B). Our previously successful
secondary phosphine oxide (SPO) ligands were also ineffective
(C),[18] because linear Ni-C≡N-Al species cannot coordinate to
both P- and O-terminus of SPO ligands, otherwise a highly
strained ring would be formed. Based on this analysis, we
envisioned to develop a new asymmetric strategy for this
reaction: using achiral mono phosphines and chiral aluminums
(D).[19] And thus, mono phosphines could ensure good reactivity,
while chiral aluminums would induce good enantioselectivity. In
consideration of low cost and easy-to-modification of both
achiral mono phosphines and chiral aluminums, the optimization
of reactivity and selectivity would be greatly facilitated.
mol%) successfully afforded the desired 3a in 39% yield and 9%
ee (Scheme 3). Encouraged by this result, a series of Taddol
derivatives[21] were then examined (L1L8), and the results
showed that bulky Taddol L8 was the best one, providing 3a in
72% yield and 22% ee. In order to further enhance
enantioselectivity, various mono phosphines were then
investigated in the presence of L8-AliBu3. Not only alkyl- or
heteroatom-substituted phosphines, but also triaryl phosphines
bearing electron-withdrawing substituted group like F on the
para-position of the aryl ring significantly retarded the reactions.
However, triaryl phosphines bearing electron-donating group
such as Me and MeO on the aryl ring greatly enhanced the ee.
For example, (4-MeOC6H4)3P gave the best result, 80% yield
and 75% ee. Notably, (2-MeOC6H4)3P still afforded good ee,
albeit with low yield. However, larger steric hindrance also
retarded subsequent insertion of the alkene. Ultimately, by using
non-polar n-hexane and lower temperature (25 C), the optimal
result was achieved (86% yield, 92% ee).
Scheme 3. Asymmetric control by chiral aluminum. Reaction conditions: 1a
(0.1 mmol), 2a (0.15 mmol), toluene (0.5 mL) under N2 for 12 h; yield was
determined by 1H NMR using CH2Br2 as the internal standard; ee was
determined by chiral HPLC. [a] n-Hexane (0.5 mL). [b] n-Hexane (0.5 mL) at
25 C for 24 h. Ar1 = 3,5-Ph2-C6H3. Ar2 = 3,5-tBu2-C6H3.
Scheme 2. Racemic reaction and strategies for asymmetric control. Reaction
conditions: 1a (0.1 mmol), 2a (0.15 mmol), toluene (0.5 mL) at 50 C under N2
for 12 h; yield was determined by 1H NMR using CH2Br2 as the internal
standard.
Under the optimized conditions, various nitriles and alkynes
were then examined (Scheme 4). Aryl nitriles bearing electron-
neutral (3a to 3d) or electron-donating groups (3e to 3g) on the
aryl ring were well tolerated, providing the corresponding
products in 6290% yield and 8695% ee, whereas electron-
withdrawing groups such as F (3h), CF3 (3i), Cl (3j) and CO2Me
(3k) significantly decreased the ee. Although bulky groups such
as tBu and aryl group on 2-position of the alkene were ineffective,
Et (3l) and functionalized linear alkyl chains (3m and 3n) worked
well, affording up to 98% ee. In addition, other symmetrical alkyl
alkynes (3o, 3p and 3q) proceeded smoothly to give the
corresponding products in 7078% yield and 9395% ee.
Following this hypothesis, we turned to explore various achiral
mono phosphines and chiral aluminums in the reaction. The
simple access to chiral aluminums is in-situ mixed chiral diols
with trialkylaluminums.[19] When Ph3P (10 mol%) was used as
achiral phosphine, a 1:1 mixture of AliBu3 (20 mol%) and (R)-
BINOL (20 mol%) was ineffective, likely owing to the formation
of dialkoxyaluminum species that has lower Lewis acidity,[20]
whereas 1:2 mixture of AliBu3 (20 mol%) and (R)-BINOL (40
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Notably, non-symmetrical aryl-alkyl alkyne produced a single
isomer (3r), probably owing to the formation of larger -
delocalization in the transition state.
of another alkyne afforded the product and regenerated Ni(0)
catalyst, and this final step also determined the reaction rate
with overall 20.9 kcal/mol energy barrier.
Scheme 5. a) DFT-calculated catalytic cycle by the achiral model b) Relative
energy and structures of Re/Si-TS2 by chiral L8. Units of energy shown in kcal
mol-1.
Scheme 4. Scope of substrates. Reaction conditions: 1 (0.2 mmol), 2 (0.3
mmol), n-Hexane (1.0 mL) under N2 for 24 h; yield for isolated products; ee
was determined by chiral HPLC. [a] 45 ºC. [b] 35 ºC.
According to the calculated mechanism, the facial chiral
selectivity should not be controlled by the low-barrier olefin
insertion step. Alternatively, the irreversible alkyne insertion step
that would lead to the determined conformation of a pro-chiral
olefin at intermediate int2 operated the enantioselectivity. We
therefore performed our computational model by using the chiral
ligand L8 for transition states of alkyne insertion, shown in
Scheme 5b. The calculated Re-TS2 is favorable and resulted
into S-product that is in agreement with experimental
observation. Through the mediating coordination of two
aluminums, the bulky Taddol L8 formed the chiral space by
pseudo chelation linking with the reaction center. This long-
range chelation was probably stabilized by the -donation of -CN
and -donation of arene group at the phosphine ligand to the Al-
Taddol species. From EDA diagram, electrostatic and dispersion
interactions dominated the favorable effect for Re-TS2,
indicating Al- interaction and crowded substitutions (i.e. -iBu)
may stabilize the transition states and determine the final major
enantiomer (see Page S23). This result is consistent with the
controlled experimental results. Substituted groups on the para
position of the aryl ring of phosphines had a direct influence on
the ee (see the Table S8). In addition, 1H NMR experiments
To gain insights into the mechanism, DFT calculations were
performed with the model reaction of 2-(prop-1-en-2-
yl)benzonitrile (1b) and but-2-yne. The initial intermediate Int0 is
formed by the coordination of triple bonds at nitrile and alkyne
with nickel center, together with the Lewis acid/base interaction
between the aluminum species and the nitrogen of nitrile group.
As outlined in Scheme 5a, the calculated mechanism starts with
the oxidative addition of CCN bond with Ni(0) assisted by
coordination of -CN with Al, and subsequent ligand exchange
formed the four coordinated Ni(II) intermediate Int1. The
favorable alkyne insertion step proceeded with aryl and CN in
the trans position, which irreversibly resulted into intermediate
Int2 with prochiral olefin coordinated with Ni(II) center,
supported by a high energy barrier of the reverse step (29.7
kcal/mol). The following insertion of olefin is rather facile (energy
barrier is only 0.4 kcal/mol), indicating that further ligand
exchange and olefin dissociation may not be favored. Finally,
the reductive elimination of the resting state Int3 in the presence
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suggested that a 1:1 mixture of L8 and AliBu3 formed three
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unreactive aluminum species (see Page S14), while a 1:2
mixture of L8 and AliBu3 formed
a
sole unsymmetrical
dialuminum species that was further deformed into
a
symmetrical structure by nitrile group of the substrate.[22] This
symmetrical aluminum species initiated CCN bond activation
and subsequent annulation.
In summary, we have developed a chiral aluminum-controlled
enantioselective nickel-catalyzed domino process for the
synthesis of various indenes bearing all-carbon quaternary
stereocenters in 3291% yield and 7398% ee. The reaction
used readily available aryl nitriles and alkynes as starting
materials, allowing efficient and atom-economical formation of
three CC bonds in one step via CCN bond activation. The
method combines inexpensive achiral phosphines with chiral
aluminums, greatly facilitating the optimization of reactivity and
selectivity. DFT calculations revealed the reaction mechanism,
indicating the irreversible alkyne insertion controls the enantio-
selectivity by a long-range chelation of Al-chiral ligand and Ni-
catalytic reaction center. Further exploring the current method in
other domino reactions involving CCN bond activation is
underway in our lab.
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Acknowledgements
We thank the National Natural Science Foundation of China
(21871145, 91856104, 21672107, 21890722 and 21702109),
the Natural Science Foundation of Tianjin Municipality
(19JCZDJC37900,
18JCYBJC21400,
19JCJQJC62300),
Tianjin Research Innovation Project for Postgraduate Students
(2019YJSB081) and “the Fundamental Research Funds for the
Central Universities”, Nankai University (63191601, 63191515,
63196021) for financial support for financial support.
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Keywords: domino • chiral aluminum • indene • quaternary
carbon • nitrile
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10.1002/anie.202001142
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Tao Zhang, Yu-Xin Luan, Su-Juan
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Chiral Aluminum-Controlled Ni-
catalyzed Enantioselective Synthesis
of Indenes via CCN Bond Activation
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