Ni(ii)/BINOL-catalyzed alkenylation of unactivated C(sp3)-H bonds

Article abstract of DOI:10.1039/c5cc02254a

The first nickel-catalyzed alkenylation of unactivated C(sp³)-H bonds with vinyl iodides is described. The catalytic system comprises an inexpensive and air-stable Ni(acac)₂ as the catalyst and BINOL as the ligand, which is highly ef

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Ni(II)/BINOL-Catalyzed Alkenylation of Unactivated C(sp3)–H Bonds
Yue-Jin Liu,a Zhuo-Zhuo Zhang,a Sheng-Yi Yan,a Yan-Hua Liu,a Bing-Feng Shi*a,b
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
5
The first nickel-catalyzed alkenylation of unactivated C(sp3)-H bonds with vinyl iodides is described. The
catalytic system comprises an inexpensive and air-stable Ni(acac)2 as catalyst and BINOL as ligand,
which is highly efficient for the alkenylation of β-methyl C(sp3)-H bonds of a broad range of aliphatic
carboxamides. The resulting olefins can serve as versatile handles for further elaboration. Additionally,
we also demonstrated the synthesis of functionalized carboxamides bearing α-quaternary carbon centers
10 from simple pivalamide via nickel-catalyzed sequential C(sp3)-H bond functionalization.
Over the past decades, transition-metal-catalyzed C-H
the viewpoints of economics and versatility.10-15 Whereas seminal
alkenylation has emerged as a versatile and powerful alternative 50 studies by Chatani,12 Ge13 and You14 have shown the success of
to the Mizoroki-Heck reaction.1,2 This transformation provides an
atom and step economical strategy for the synthesis of
15 functionalized olefins. The alkenylation of (hetero)aryl C(sp2)-H
bonds catalyzed by a variety of metal catalysts, such as Pd, Rh,
nickel-catalyzed arylation and alkylation of unactivated C(sp3)-H
bonds employing 8-aminoquinoline (AQ) as N,N-bidentate
directing group,16 no example of nickel-catalyzed C(sp3)-H
alkenylation has been reported.17,18 The chief barriers to C(sp3)-H
Ru, Cu, Co and Ni, has been well investigated.2 These 55 alkenylation compared to the analogous arylation and alkylation
transformations have also been applied to the total synthesis and
late-stage functionalization of natural products and drug
20 molecules.3,4 In contrast, the direct alkenylation of unactivated
C(sp3)-H bonds remains a great challenge, largely due to the
are at least twofold: 1) the competitive coordination of the
alkenylation reagents may inhibit the activation of C(sp3)-H
bonds; 2) the resulting alkene and the intrinsic bidentate auxiliary
may coordinate with nickel catalyst to form a thermodynamically
inherent low reactivity of aliphatic C(sp3)-H bonds5 and the 60 stable tridentate complex and shut down the reaction.
competitive coordination of the olefins to interfere with the C-H
functionalization reaction.6 So far, only a few examples of such
25 transformations have been reported (Scheme 1A). In 2010, Yu
and coworkers reported a Pd-catalyzed olefination of β-methyl
C(sp3)-H bonds with acrylates directed by a weakly coordinating
N-arylamide (CONHAr) directing group.7a,b More recently, they
have extended this dehydragenative olefination protocol to γ-
30 C(sp3)-H bonds promoted by a quinoline-based ligand.7c The
Sanford group reported a Pd/polyoxometalate-catalyzed pyridyl-
directed C(sp3)-H olefination with acrylates.7d However, the
expected alkenylated products could not be isolated due to the
intramolecular Michael addition to give the corresponding
35 cyclization products. Recently, the direct alkenylation of
unactivated C(sp3)-H bonds with vinyl iodides8 has been reported
by Baran9a,b and Chen9c,d
synthesized through these protocols. In particular, the Baran
group has demonstrated the total synthesis of
. The desired olefins could be
Scheme 1. Transition-metal-catalyzed alkenylation of C(sp3)–H
bonds.
40 Pipercyclobutanamide A by the use of this alkenylation reaction
as a key step.9b While considerable progress has been achieved,
these methods are limited to the use of noble metal palladium as
catalyst and very specific substrates. Therefore, the development
of a general and efficient protocol for the alkenylation of
45 unactivated C(sp3)–H bonds using low-cost metal catalysts would
be very challenging and extremely attractive.
As part of our continuous program on functionalization of
65 unactivated C(sp3)-H bonds,19 we became interested in
developing methods for the alkenylation of aliphatic C(sp3)-H
bonds in consideration of the great challenges associated. Here
we describe a novel catalyst system that allows for efficient
alkenylation of β-methyl C(sp3)-H bonds of a broad range of
70 aliphatic carboxamides (Scheme 1B). The synthetic utility of this
protocol is further demonstrated by the synthesis of
Recently, nickel has been identified as a powerful and
promising catalyst for the functionalization of C-H bonds from
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functionalized carboxamides bearing α-quaternary carbon centers
from simple pivalamide via nickel-catalyzed sequential C(sp3)-H
bond functionalization.
conditions, the corresponding alkenylated product 3l was
obtained in 57% yield, with the aryl bromide remaining intact.
The orthogonal reactivity of the C-H alkenylation and bromo
We initially examined the alkenylation of carboxamide 1a with 40 groups provides a useful opportunity for further elaboration of the
5
styrenyl iodide 2a. At the outset, we were pleased to find that the
desired alkenylated product 3a was obtained in 23% yield by
using 10 mol% Ni(acac)2 and BDMAE with Na2CO3 as base in
DMSO under atmosphere of N2 (Table 1, entry 1). Further
screening revealed that the combination of Ni(acac)2 and KTFA
olefin products by traditional cross-coupling.
10 was the optimal (entry 4). Extensive investigation of a number of
privileged ligands that often used in nickel catalysts, such as
phosphines and amines, provided little improvement in yield
(entries 4-10, for detailed screening, see SI). Instead, a series of
diol-type ligands showed superior reactivity (entries 11-15). Use
15 of BINOL (L3) provided the best results and gave the desired
products 3a in 73% yield (entry 12). The yield was further
improved to 78% when a combination of KTFA and Li2CO3 with
40 mol% BINOL was used (entry 16).
Table 1. Optimization of the reaction conditionsa
20
Entry
Ligand
Base
Yield (%)b
1
2
3
4
5
BDMAE
BDMAE
BDMAE
BDMAE
PPh3
Na2CO3
Li2CO3
K2CO3
KTFA
KTFA
23
11
8
25
9
6
7
8
9
10
11
12
13
14
15
16c
dppb
KTFA
KTFA
KTFA
KTFA
KTFA
KTFA
KTFA
KTFA
13
10
17
trace
34
38
73
63
58
48
78d
BINAP
TMEDA
1,10-Phen
L1
Scheme 2. The scope of styrenyl iodides. Reaction conditions: 1a
(0.1 mmol), 2 (0.2 mmol), Ni(acac)2 (10 mol%), BINOL (40
45 mol%), Li2CO3 (0.2 mmol), KTFA (0.2 mmol) in 1.0 mL DMSO,
140 oC, under N2, 8 h, isolated yield.
L2
L3
L4
L5
L6
L3
KTFA
KTFA
KTFA + Li2CO3
The scope of carboxamides was explored next. We found that
a wide variety of carboxamides bearing both linear and cyclic
chains were compatible with this protocol (Scheme 3). However,
50 consistent with previous reports, a quaternary α-carbon is
necessary for the success of this reaction.12-14 Notably, vinyl
functional group was tolerated and gave the corresponding
divinyl products 4i in moderate yield. In addition, the selective
activation of β-methyl C(sp3)-H bonds over γ-aromatic C(sp2)-H
55 bonds was observed when 2-phenyl-substituted carboxamides (1i-
1o) were used.
aReaction conditions: 1a (0.1 mmol), [Ni] (10 mol%), Ligand (20 mol%), base (2.0
equiv) in DMSO (1 mL) at 140 oC for 8 h under N2. b1H NMR yields using CH2Br2
as the internal standard. c40 mol% L3 was used. dIsolated yield. AQ = 8-quinolinyl,
25 BDMAE = bis(2-dimethylaminoethyl)ether, DME = dimethoxyethane, TFA =
trifluoroacetoxyl.
The scope of this alkenylation protocol was first examined by
varying the vinyl iodides. As shown in Scheme 2, both electron-
deficient and electron-rich E-β-iodostyrenes reacted smoothly
30 with carboxamide 1a to exclusively give the E-isomers 3 in
moderate to good yields.20 Substituents at the ortho-, meta-, or
para-positions of the styrene were tolerated. Various functional
groups were tolerated under the optimized reaction conditions,
including fluoro (3d), methoxy (3e), cyano (3f), chloro (2g and 3i)
35 and trifluoromethyl (3k). Moreover, when styrenyl iodide bearing
a m-bromo substituent was subjected to the standard reaction
2
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functionalization. Reagents and conditions: a) ArI, Ni(OTf)2 ( 10
20 mol%), MesCO2H (20 mol%), Na2CO3, DMF, 140 oC; b) i) vinyl
iodide, Ni(acac)2 (10 mol%), BINOL (40 mol%), Li2CO3, KTFA
o
o
DMSO, 140 C, 62% yield; ii) Pd/C, HCO2NH4, MeOH, 80 C,
92% yield; c) vinyl iodide, Ni(acac)2 (10 mol%), BINOL (40
mol%), Li2CO3, KTFA DMSO, 140 oC, 72% yield.
25
Finally, further functionalization of the resulting olefin-
containing products was demonstrated. As shown in Scheme 5,
4k was readily dihydroxylated to give the corresponding diol 8 in
85% yield (dr = 1:1). The hydrogenation of 4k also proceeded
30 smoothly to give 9 in 78% yield.
Scheme 5. Functionalization of C–H alkenylated product 4k.
Scheme 3. The scope of aliphatic carboxamides. Reaction
conditions: 1 (0.1 mmol), 2e (0.2 mmol), Ni(acac)2 (10 mol%),
BINOL (40 mol%), Li2CO3 (0.2 mmol), KTFA (0.2 mmol) in 1.0
mL DMSO, 140 oC, under N2, 8 h, isolated yield.
In conclusion, we have developed a novel nickel-catalyzed
direct alkenylation of unactivated C(sp3)-H bonds with styrenyl
35 iodides employing AQ as a bidentate directing group. The
reaction is accomplished by an inexpensive and air-stable
catalytic system consisting of Ni(acac)2 and unusual BINOL as
ligand. A wide variety of functional groups were tolerated under
the optimized reaction conditions. The synthesis of functionalized
40 carboxamides bearing α-quaternary carbon centers from simple
pivalamide via Ni-catalyzed sequential C(sp3)-H bonds
functionalization was also demonstrated. Efforts to expand the
scope of this transformation to other types of substrates and
elucidate mechanistic details are underway.21
5
To demonstrate the utility of this alkenylation protocol, the
synthesis of functionalized carboxamides 7 bearing α-quaternary
carbon centers from pivalamide 1d via Ni-catalyzed sequential
C(sp3)-H bonds functionalization was developed. As shown in
10 Scheme 4, nickel-catalyzed arylation of pivalamide 1d proceeded
smoothly to give arylated product 5.12a Subsequently, 5 was
subjected to our alkenylation protocol followed by hydrogenation
to furnish compound 6, which was reacted with styrenyl iodide
under the standard alkenylation conditions to afford
15 carboxamides 7.
45 Acknowledgements
Financial support from the National Basic Research Program of China
(2015CB856600), the NSFC (21422206, 21272206) and the Fundamental
Research Funds for the Central Universities is gratefully acknowledged.
Notes and references
50 aDepartment of Chemistry, Zhejiang University, Hangzhou 310027,
China. E-mail: bfshi@zju.edu.cn
bState Key Laboratory of Bioorganic & Natural Products Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China
55 † Electronic Supplementary Information (ESI) available: Detailed
experimental procedures, and analytical data for all new compounds, see
DOI: 10.1039/b000000x/
‡ Footnotes should appear here. These might include comments relevant
to but not central to the matter under discussion, limited experimental and
60 spectral data, and crystallographic data.
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Scheme 4. Synthesis of highly functionalized carboxamide 7
from pivalamide 1d via Ni-catalyzed sequential C-H
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The first nickel-catalyzed alkenylation of unactivated C(sp3)-H bonds with vinyl iodides is described.
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