Iridium-Catalyzed Asymmetric Hydroalkenylation of Norbornene Derivatives

Article abstract of DOI:10.1021/acs.organomet.0c00811

Transition-metal-catalyzed asymmetric hydroalkenylation of alkenes provides an atom-economical method to build molecular complexity from easily available materials. Herein we report an iridium-catalyzed asymmetric hydroalkenylation of unconjugated alkenes with acrylamides and acrylates. The catalytic hydroalkenylation of norbornene derivatives occurred to form products with allylic stereocenters with high chemo-, regio-, and stereoselectivities. DFT calculations revealed that the migratory insertion is irreversible and the enantiodetermination step.

Full text of DOI:10.1021/acs.organomet.0c00811

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Iridium-Catalyzed Asymmetric Hydroalkenylation of Norbornene
Derivatives
Xin Sun, Xiao-Yan Bai,* An-Zhen Li, and Bi-Jie Li*
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ABSTRACT: Transition-metal-catalyzed asymmetric hydroalke-
nylation of alkenes provides an atom-economical method to
build molecular complexity from easily available materials. Herein
we report an iridium-catalyzed asymmetric hydroalkenylation of
unconjugated alkenes with acrylamides and acrylates. The catalytic
hydroalkenylation of norbornene derivatives occurred to form
products with allylic stereocenters with high chemo-, regio-, and stereoselectivities. DFT calculations revealed that the migratory
insertion is irreversible and the enantiodetermination step.
a
Table 1. Reaction Development
he transition-metal-catalyzed Mizoroki−Heck reaction is
1
Ta powerful method to construct C−C bonds. However,
coupling of alkyl halides with terminal alkenes is difficult
because of the slow oxidative addition and potential side
reactions (Scheme 1a).2 In particular, catalytic enantioselective
coupling of secondary alkyl halides with terminal alkenes
remains an important synthetic challenge (Scheme 1b).3 This
process produces useful chiral products containing an allylic
stereocenter. Therefore, alternative processes to access these
chiral products from alkenes are highly desirable.
Transition-metal-catalyzed asymmetric hydroalkenylation of
alkenes provides an atom-economical method to generate
these chiral products from easily available alkene substrates
Scheme 1. Challenge of the Mizoroki−Heck Reaction and
Hydroalkenylation of Alkenes
a
Reaction conditions: 1a (0.10 mmol), 2a (0.20 mmol), Ir-
(COD)2OTf (5 mol %, 0.0050 mmol), ligand (6 mol %, 0.0060
mmol), DCE (0.50 mL), 80 °C, 14 h. Yields were determined by
b
NMR spectroscopy using CH2Br2 as an internal standard. Isolated
yield.
Special Issue: Organometallic Solutions to Challenges
in Cross-Coupling
Received: December 29, 2020
https://dx.doi.org/10.1021/acs.organomet.0c00811
© XXXX American Chemical Society
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A

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a
a
Table 2. Substrate Scope for Norbornene Derivatives
Table 3. Substrate Scope for Acrylamide Derivatives
a
Reaction conditions: 1a (0.10 mmol), 2a−i (0.20 mmol),
Ir(COD)2OTf (5 mol %, 0.0050 mmol), L8 (6 mol %, 0.0060
mmol), DCE (0.50 mL), 80 °C, 14 h. Isolated yields are reported. 2b
(0.50 mmol). 2c (0.50 mmol).
b
c
(Scheme 1c).4 Since the first example of asymmetric
hydrovinylation reported in 1972,5 catalytic asymmetric
hydrovinylations6 of styrenes,7 conjugated alkenes,8 and
strained alkenes9 with ethylene have been reported. In
contrast, asymmetric hydroalkenylations involving substituted
alkenes are less developed. In such an enantioselective alkene
dimerization process, the two alkenes must chemoselectively
react with each other. In addition, the regioselectivities on both
alkenes and the enantioselectivity of the process must be
effectively controlled. Currently, catalytic asymmetric hydro-
alkenylations using substituted alkenes have been developed
mainly for conjugated alkenes such as styrenes10 and 1,3-
dienes.11 Recently, Hirano described a Ru-catalyzed asym-
metric hydroalkenylation of 2,5-dihydrofuran with acrylates to
afford the coupling products with good enantioselectivity.12
We report here an iridium-catalyzed highly enantioselective
coupling of unconjugated alkenes with acrylamides to afford
products containing three stereocenters (Scheme 1d).13,14 In
the presence of a coordinating group, the low-valent cationic
iridium species selectively cleaves the vinyl C−H bond.15,16
Further reaction of the vinyliridium intermediate with
norbornene generates the hydrovinylation products with high
chemo-, regio-, and stereoselectivities. This mechanism is
distinct from those in previous reports on hydroalkenylation of
conjugated alkenes.10−12 The catalytic system is applicable to a
variety of acrylamide and norbornene derivatives. Further
computational studies revealed the origin of the enantiose-
lectivity.
a
Reaction conditions: 1a−l (0.10 mmol), 2e (0.20 mmol),
Ir(COD)2OTf (5 mol %, 0.005 mmol), L8 (6 mol %, 0.0060
mmol), DCE (0.50 mL), 80 °C, 14 h. Isolated yields are reported.
We began our study by testing the hydroalkenylation
between α,β-unsaturated amide 1a and benzonorbornadiene
(2a) in the presence of Ir(COD)2OTf and a series of chiral
ligands (Table 1). When Du-Phos (L1), DIOP (L2), or a
phosphoramidite (L3) was used, no hydroalkenylation product
was observed. However, with Josiphos (L4) or SDP (L5) as
the ligand, the desired product was observed, although in low
yield with moderate enantioselectivity. The product could be
obtained in high yield and enantioselectivity with BINAP (L6)
as the ligand. Further variations of the ligand backbone
indicated that Difluorphos (L8) provided even higher ee in the
hydroalkenylation reaction. Importantly, only the Z isomer was
obtained for the hydroalkenylation product. This is supportive
of a directed C−H cleavage mechanism, as only the C−H
bond cis to the coordinating group was cleaved (vide infra). In
addition, the high Z selectivity indicates minimal alkene
isomerization in the catalytic system, although an iridium
hydride intermediate was involved.
The substrate scope of the asymmetric hydroalkenylation
reaction was subsequently investigated (Table 2). The
reactions of norbornene and norbornadiene afforded the
B
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Communication
Figure 1. Computational studies for catalytic hydroalkenylation. (A) Energy profile for catalytic hydroalkenylation. (B) Structures of key transition
states. Calculations were carried out at the M06/6-311++G(d,p)/SDD//B3LYP/6-31G(d,p)/LANL2DZ level of theory.
corresponding products 3ab and 3ac in high yields with high
ee’s. The absolute configuration of 3ab was determined by
subsequent derivatization and comparison with authentic
samples (see the Supporting Information).9a Both electron-
donating and electron-withdrawing groups on the benzonor-
bornadiene were tolerated (3ad−ah). Catalytic hydroalkeny-
lation of 1,4-epoxy-1,4-dihydronaphthalene provided the
product 3ai in high yield, although the ee value was low (see
the Supporting Information for discussion).
To gain insight into the reaction mechanism, computational
studies were conducted (Figure 1). The reaction starts with the
oxidative addition of the alkenyl C−H of the acrylamide (Int-
0) to afford an alkenyliridium hydride intermediate (Int-1)
with coordination of the carbonyl group (Figure 1A). After
coordination of norbornene to the iridium center of Int-1, the
CC bond of norbornene undergoes migratory insertion into
the Ir−C bond to generate an iridacycle. Finally, C−H bond-
forming reductive elimination delivers the hydroalkenylation
product. The activation free energies in the reaction profile
indicate that migratory insertion (TS-2b vs TS-2a) is
irreversible and determines the enantioselectivity. The
transition state leading to the major enantiomer (TS-2b) has
an activation barrier of 25.0 kcal·mol−1 while the competing
transition state (TS-2a) has an activation free energy of 29.9
kcal·mol−1. Thus, the product was predicted to be formed with
>99% ee. The predicted absolute configuration and high
enantioselectivity are in good agreement with the experimental
results.
We further tested the scope of various acrylamides (Table
3). The reaction was applicable to substrates derived from both
acyclic amines (3ae−ce) and cyclic amines (3de and 3ee). The
acrylamide with an α-methyl group underwent the hydro-
alkenylation smoothly and generated the product in high yield
with high ee (3fe). In addition to tertiary acrylamides,
secondary acrylamides were tolerated (3ge−le). We found
that the substituents on the nitrogen had an influence on the
ee value. The product was obtained with higher enantiose-
lectivity for an N-alkylamide (3ke) than for N-arylamides (3ie
and 3je). Functional groups including aryl halides and
thiophene were tolerated.
In addition to acrylamides, acrylates underwent efficient
hydroalkenylation. For example, catalytic hydroalkenylation of
norbornene with n-butyl acrylate afforded product 5ab with
high enantioselectivity, although a higher catalyst loading was
necessary (eq 1).
Analysis of the two competing transition state structures
revealed the origin of the enantioselectivity (Figure 1B). In TS-
2a, the vinylic C−H bond of norbornene experiences repulsion
C
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In summary, we have developed an iridium-catalyzed
asymmetric hydroalkenylation reaction of unconjugated
alkenes with acrylamides and acrylates. The catalytic hydro-
alkenylation of norbornene derivatives occurred in high yields
with high diastereo- and enantioselectivities. DFT calculations
revealed that the migratory insertion is irreversible and the
enantiodetermining step. Further expansion of the substrate
scope and investigation of the detailed mechanism are
currently ongoing in our laboratory.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.organomet.0c00811.
■
sı
Experimental procedures, characterization data for new
compounds, and spectroscopic data (PDF)
Cartesian coordinates (XYZ)
AUTHOR INFORMATION
Corresponding Authors
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in the Catalytic Linear Cross-Dimerizations. ACS Catal. 2019, 9,
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■
Bi-Jie Li − Center of Basic Molecular Science (CBMS),
Department of Chemistry, Tsinghua University, Beijing
100084, China; orcid.org/0000-0001-8528-8514;
Email: bijieli@mail.tsinghua.edu.cn
́
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Catalyzed Asymmetric Synthesis. Angew. Chem., Int. Ed. Engl. 1972,
11, 1023−1024.
Xiao-Yan Bai − College of Chemistry and Material Science,
Sichuan Normal University, Chengdu, Sichuan 610066,
China; Email: baixy@sicnu.edu.cn
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Olefins. Synlett 2009, 2009, 853−885.
̈
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Authors
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Amenable to Asymmetric Catalysis. J. Am. Chem. Soc. 1998, 120,
459−460. (c) Albert, J.; Cadena, J. M.; Granell, J.; Muller, G.;
Xin Sun − Center of Basic Molecular Science (CBMS),
Department of Chemistry, Tsinghua University, Beijing
100084, China
An-Zhen Li − Center of Basic Molecular Science (CBMS),
Department of Chemistry, Tsinghua University, Beijing
100084, China
Ordinas, J. I.; Panyella, D.; Puerta, C.; Sanudo, C.; Valerga, P.
̃
Resolution of Benzylcyclohexylphenylphosphine by Palladium(II)−
Complete contact information is available at:
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Amine Metallacycles. A New Ligand for Asymmetric Hydrovinylation.
̀
Organometallics 1999, 18, 3511−3518. (d) Francio, G.; Faraone, F.;
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Diarylphosphinites Induce High Selectivity in the Hydrovinylation
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(f) RajanBabu, T. V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X.
Heterodimerization of Olefins. 1. Hydrovinylation Reactions of
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for the financial support from the National
Natural Science Foundation of China (91856107 and
22022104).
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