G
Synlett
S. Thiyagarajan, C. Gunanathan
Synpacts
H
M. J. Med. Chem. 2009, 52, 5020. (d) Walter, M. W. Nat. Prod. Rep.
H
2002, 19, 278. (e) Smith, M. B.; March, J. March’s Advanced
N
PPh2
CO
Organic Chemistry: Reactions, Mechanisms, and Structure, 6th
ed; Wiley-Interscience: Hoboken, 2007.
Ru
Cl
P
Ph2
(2) (a) Caine, D. In Comprehensive Organic Synthesis, Vol. 3; Trost, B.
M.; Fleming, I., Ed.; Pergamon: Oxford, 1991, Chap. 1.1, 1–63.
(b) Reetz, M. T. Angew. Chem., Int. Ed. Engl. 1982, 21, 96.
3) (a) Parthasarathy, G.; Hart, R.; Jamro, E.; Miner, L. Clean Technol.
Environ. Policy 2005, 7, 219. (b) Metzger, J. O.; Eissen, M. C. R.
Chim. 2004, 7, 569. (c) Jenck, J. F.; Agterberg, F.; Droescher, M. J.
Green Chem. 2004, 6, 544.
4) (a) Huang, F.; Liu, Z.; Yu, Z. Angew. Chem. Int. Ed. 2016, 55, 862.
(b) Obora, Y. Top. Curr. Chem. 2016, 374, 1. (c) Obora, Y. ACS
Catal. 2014, 4, 3972.
–
KCl
t
t
KO Bu
–
BuOH
(
H
OH
R
OH
N
PPh2
Ru
(
P
CO
Ph2
I
(5) For reviews on borrowing-hydrogen methodology, see:
(a) Corma, A.; Navas, J.; Sabater, M. J. Chem. Rev. 2018, 118,
H2
1
410. (b) Faisca Phillips, A. M.; Pombeiro, A. J. L.; Kopylovich, M.
O
N. ChemCatChem 2017, 9, 217. (c) Chelucci, G. Coord. Chem. Rev.
2017, 331, 1. (d) Yang, Q.; Wang, Q.; Yu, Z. Chem. Soc. Rev. 2015,
H
H
R
H
N
H
44, 2305. (e) Nandakumar, A.; Midya, S. P.; Landge, V. G.;
PPh2
CO
N
PPh2
CO
Balaraman, E. Angew. Chem. Int. Ed. 2015, 54, 11022.
(f) Ketcham, J. M.; Shin, I.; Montgomery, T. P.; Kriche, M. J.
Angew. Chem. Int. Ed. 2014, 53, 9142. (g) Pan, S.; Shibata, T. ACS
Catal. 2013, 3, 704. (h) Obora, T. D.; Ishii, Y. Synlett 2011, 2011,
30. (i) Bähn, S.; Imm, S.; Neubert, L.; Zhang, M.; Neumann, H.;
Beller, M. ChemCatChem 2011, 3, 1853. (j) Dobereiner, G. E.;
Crabtree, R. H. Chem. Rev. 2010, 110, 681. (k) Guillena, G.;
Ramón, D. J.; Yus, M. Chem. Rev. 2010, 110, 1611. (l) Watson, A. J.
A.; Williams, J. M. J. Science 2010, 329, 635. (m) Nixon, T. D.;
Whittlesey, M. K.; Williams, J. M. J. Dalton Trans. 2009, 753.
(n) Hamid, M. H. S. A.; Slatford, P. A.; Williams, J. M. J. Adv. Synth.
Catal. 2007, 349, 1555. (o) Guillena, G.; Ramón, D. J.; Yus, M.
Angew. Chem. Int. Ed. 2007, 46, 2358.
Ru
P
Ru
O
P
Ph2
O
Ph2
O
II
R
II'
R
C
base
H2O
A + B
H
O
O
H
N
PPh2
CO
R
Ru
H
P
A
Ph2
B
(
6) For reviews on acceptorless dehydrogenation of alcohols, see:
III
(
(
a) Crabtree, R. H. Chem. Rev. 2017, 117, 9228.
b) Khusnutdinova, J. R.; Milstein, D. Angew. Chem. Int. Ed. 2015,
Scheme 8 Proposed catalytic cycle for the cross-coupling of secondary
alcohols. (Reprinted with permission from reference 12. © 2019, Amer-
ican Chemical Society.)
54, 12236. (c) Gunanathan, C.; Milstein, D. Chem. Rev. 2014, 114,
12024. (d) Gunanathan, C.; Milstein, D. Science 2013, 341,
1229712. (e) Gunanathan, C.; Milstein, D. Acc. Chem. Res. 2011,
green catalytic protocol. This new cross-coupling reaction
protocol will be an important development in the synthesis
of -disubstituted ketones, and should be applicable to lab-
oratory and industrial-scale chemical syntheses.
44, 588.
(
7) (a) Das, U. K.; Ben-David, Y.; Leitus, G.; Diskin-Posner, Y.;
Milstein, D. ACS Catal. 2019, 9, 479. (b) Paudel, K.; Pandey, B.;
Xu, S.; Taylor, D. K.; Tyer, D. L.; Torres, C. L.; Gallagher, S.; Kong,
L.; Ding, K. Org. Lett. 2018, 20, 4478. (c) Nielsen, M.; Junge, H.;
Kammer, A.; Beller, M. Angew. Chem. Int. Ed. 2012, 51, 5711.
(
(
d) Sølvhøj, A.; Madsen, R. Organometallics 2011, 30, 6044.
e) Gnanaprakasam, B.; Ben-David, Y.; Milstein, D. Adv. Synth.
Funding Information
Catal. 2010, 352, 3169. (f) Gunanathan, C.; Shimon, L. J. W.;
Milstein, D. J. Am. Chem. Soc. 2009, 131, 3146. (g) Zhang, J.;
Leitus, G.; Ben-David, Y.; Milstein, D. J. Am. Chem. Soc. 2005, 127,
We thank SERB New Delhi (EMR/2016/002517), DAE, and NISER for
financial support.
S
c
i
e
n
c
e
a
n
d
E
n
g
i
n
e
eri
n
g
R
esearc
h
B
o
ard (E
M
R/2
0
1
6/0
0
2
5
1
7)
10840.
(
8) (a) Chakraborty, S.; Daw, P.; Ben-David, Y.; Milstein, D. ACS
Catal. 2018, 8, 10300. (b) Tan, D.-W.; Li, H.-X.; Zhu, D.-L.; Li, H.-
Y.; Young, D. J.; Yao, J.-L.; Lang, J.-P. Org. Lett. 2018, 20, 608.
(c) Sahoo, A. R.; Lalitha, G.; Murugesh, V.; Bruneau, C.; Sharma,
G. V. M.; Suresh, S.; Achard, M. J. Org. Chem. 2017, 82, 10727.
Acknowledgment
S.T. thanks UGC for a research fellowship. We thank Professor J. V.
Yeldho for his kind help.
(d) Jiménez, M. V.; Fernández-Tornos, J.; Modrego, F. J.; Pérez-
References
Torrente, J. J.; Oro, L. A. Chem. Eur. J. 2015, 21, 17877.
9) (a) Aitchison, H.; Wingad, R. L.; Wass, D. F. ACS Catal. 2016, 6,
7125. (b) Xie, Y.; Ben-David, Y.; Shimon, L. J. W.; Milstein, D.
J. Am. Chem. Soc. 2016, 138, 9077. (c) Kozlowski, J. T.; Davis, R. J.
ACS Catal. 2013, 3, 1588.
(
(
1) (a) Toh, Q. Y.; McNally, A.; Vera, S.; Erdmann, N.; Gaunt, M. J.
J. Am. Chem. Soc. 2013, 135, 3772. (b) Maeyama, K.; Yamashita,
K.; Saito, H.; Aikawa, S.; Yoshida, Y. Polym. J. (Tokyo) 2012, 44,
315. (c) Vooturi, S. K.; Cheung, C. M.; Rybak, M. J.; Firestine, S.
©
2019. Thieme. All rights reserved. — Synlett 2019, 30, A–H