10.1002/anie.201907185
Angewandte Chemie International Edition
COMMUNICATION
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For selected reviews, see: a) W. L. A. Brooks, B. S. Sumerlin, Chem.
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Hall), Wiley-VCH, Weinheim, 2011.
a) Competition experiments of regioselectivity: benzylic versus α-carbon of alkylboronate
Ph
standard
3n'
Bpin
80% yield, >99:1 rr
conditions
PMP
(1.0 D)
Bpin
Bpin
+
PMP
I
Ph
Ph
Ph
DBpin
used
1n
2b
3n'-D
74% yield, >99:1 rr
PMP
PMP
()4 Bpin
[2]
[3]
For selected reviews, see: a) C. M. Crudden, B. W. Glasspoole, C. J.
Lata, Chem. Commun. 2009, 6704; b) R. Jana, T. P. Pathak, M. S.
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Chem. Commun. 2017, 53, 5481.
PMP
+
standard
Bpin
+
PMP
2b
I
()3
Ph
Bpin
()4
conditions
Ph
1o
3o 33% yield
3o' 30% yield
For selected reviews, see: a) H. C. Brown, B. Singaram, Acc. Chem.
Res. 1988, 21, 287; b) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M.
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2019, 75, 584.
(<0.10 D)
(0 D)
(<0.10 D)
(0.77 D)
PMP
PMP
(0 D)
Ph
(0.32 D)
DBpin
used
+
Ph
(0.36 D)
Bpin
H
b(0.36 D)
Bpin
H
(0.58 D)
a
3o-D 13% yield
b) Synthetic utility: derivatization of α-aryl alkylboronate esters
3o'-D 39% yield
Ph
OH
Ph
NaBO3·4H2O
LiCH2Cl
then
Bpin
1a
OH
nPr
nPr
THF/H2O
(6.0 mmol scale)
NaOH, H2O2
5a 86% yield
5d 72% yield
S
Ph
Ph
Li
Ph
BrMg
nPr
Bpin
[4]
For selected examples using α-haloboranes, see: a) J. Schmidt, J. Choi,
A. T. Liu, M. Slusarczyk, G. C. Fu, Science 2016, 354, 1265; b) S.-Z.
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Börjesson, R. Martin-Montero, R. Martin, J. Am. Chem. Soc. 2018, 140,
12765. Selected examples using 1,1-diborylalkanes, see: d) K. Endo, T.
Ohkubo, M. Hirokami, T. Shibata, J. Am. Chem. Soc. 2010, 132, 11033;
e) J. C. H. Lee, R. McDonald, D. G. Hall, Nat. Chem. 2011, 3, 894; f) X.
Feng, H. Jeon, J. Yun, Angew. Chem. Int. Ed. 2013, 52, 3989; g) C.
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6176; i) Z.-Q. Zhang, C.-T. Yang, L.-J. Liang, B. Xiao, X. Lu, J.-H. Liu,
Y.-Y. Sun, T. B. Marder, Y. Fu, Org. Lett. 2014, 16, 6342. Selected
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Hall, J. Am. Chem. Soc. 2010, 132, 5544; k) J. Li, M. D. Burke, J. Am.
Chem. Soc. 2011, 133, 13774; l) D. Nishikawa, K. Hirano, M. Miura, J.
Am. Chem. Soc. 2015, 137, 15620; m) J. T. Han, W. J. Jang, N. Kim, J.
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J. N. Harvey, V. K. Aggarwal, Nature 2014, 513, 183.
S
nPr
nPr
then
then NBS
OMe
3a (1.18 g)
76% yield, 97:3 rr
5e
I2, MeOH
5b 58% yield
w/o isolation
versatile precursor
OMe
Ph
I
9-BBN
Ph
nPr
then
NaOH, H2O2
OH
Pd2(dba)3, PPh3
Ag2O, THF, 80 o
nPr
5c 51% yield
5e' 59% yield
for two steps
C
c) Preliminary result of enantioselective reaction
5 mol% NiCl2·6H2O, 7 mol% L3
2.0 equiv KF, 2.5 equiv PMHS
Ph
nBu
+
Ph I
Bpin
nPent
Bpin
DMA (0.40 M), 0 o
C
1g (1.0 equiv)
2a (2.0 equiv)
(R)-3g
O
O
76% yield, >99:1 rr
62% ee
L3:
N
N
Cy
Cy
Scheme 1. Competition experiments, synthetic utility, and preliminary result of
enantioselective conversion.
In summary, based on the NiH-catalyzed remote
hydrofunctionalization platform, we have established a practical
and efficient remote hydroarylation process forming α-
functionalized alkylboronates, from simple boron-containing
olefins and commercially available cross-coupling partners. With
the mild conditions used, excellent chemo- and regioselectivity
was observed for a wide range of both alkene and aryl iodide
partners. Further studies on the catalytic asymmetric version of
the current transformation based on ligand design are in
progress.
[5]
[6]
For reviews on remote functionalization through alkene isomerization,
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Acknowledgements
Support was provided by NSFC (21822105).
Keywords: arylation • C–H activation • isomerization • nickel •
regioselectivity
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