Communication
ChemComm
MHB and GRK thank CSIR for the fellowships. We thank
SAIF division CSIR-CDRI for the analytical support. We grate-
fully acknowledge the financial support from CSIR-THUNDER
(BSC 0102). CDRI Communication No: 9460.
Notes and references
1 For Wittig olefination, see: (a) B. E. Maryanoff and A. B. Reitz, Chem.
Rev., 1989, 89, 863; (b) X. Tong and J. Kallmerten, Synlett, 1992, 845;
(c) D.-J. Dong, H.-H. Li and S.-K. Tian, J. Am. Chem. Soc., 2010,
132, 5018; (d) S. Sano, T. Takehisa, S. Ogawa, K. Yokoyama and
Y. Nagao, Chem. Pharm. Bull., 2002, 50, 1300; (e) T. Umezawa,
T. Seino and F. Matsuda, Org. Lett., 2012, 14, 4206.
2 For McMurry reaction, (a) C. Villiers and M. Ephritikhine, Angew.
Chem., Int. Ed. Engl., 1997, 36, 2380; (b) M. Ephritikhine, Chem.
Commun., 1998, 2549; and references therein.
Scheme 8 Tetrasubstituted olefins via carboarylation.
3 (a) C. C. C. J. Seechurn, M. O. Kitching, T. J. Colacot and V. Snieckus,
Angew. Chem., Int. Ed., 2012, 51, 5062; (b) T. Mizoroki, K. Mori and
A. Ozaki, Bull. Chem. Soc. Jpn., 1971, 44, 581; (c) R. F. Heck and
J. P. Nolley Jr., J. Org. Chem., 1972, 37, 2320; (d) R. F. Heck, Org.
React., 1982, 27, 345; (e) L. Yin and J. Liebscher, Chem. Rev., 2007,
107, 133; ( f ) Y. Fujiwara, I. Moritani, S. Danno, R. Asano and
S. Teranishi, J. Am. Chem. Soc., 1969, 91, 7166; (g) C. Jia, D. Piao,
J. Oyamada, W. Lu, T. Kitamura and Y. Fujiwara, Science, 2000,
287, 1992.
4 (a) P. R. Blakemore, W. J. Cole, P. J. Kocienski and A. Morley, Synlett,
1998, 26; (b) J. Pospisil and I. E. Marko, Org. Lett., 2006, 8, 5983;
(c) G. E. Keck, K. A. Savin and M. Weglarz, J. Org. Chem., 1995,
60, 3194; (d) M. Shindo, K. Matsumoto, S. Mori and K. Shishido,
J. Am. Chem. Soc., 2002, 124, 6840; (e) T.-L. Chan, S. Fong, Y. Li,
T.-O. Man and C.-D. Poon, J. Chem. Soc., Chem. Commun., 1994,
1771; ( f ) A. C. Bissember, A. Levina and G. C. Fu, J. Am. Chem. Soc.,
2012, 134, 14232.
Scheme 9 Mechanism for Ni-catalyzed hydroarylation.
5 (a) T. Hayashi, K. Inoue, N. Taniguchi and M. Ogasawara, J. Am.
Chem. Soc., 2001, 123, 9918; (b) X. Xu, J. Chen, W. Gao, H. Wu,
J. Ding and W. Su, Tetrahedron, 2010, 66, 2433; (c) E. Shirakawa,
G. Takahashi, T. Tsuchimoto and Y. Kawakami, Chem. Commun.,
2001, 2688; (d) Y. Yamamoto, N. Kirai and Y. Harada, Chem.
Commun., 2008, 2010; (e) P. S. Lin, M. Jeganmohan and C. H.
Cheng, Chem. – Eur. J., 2008, 14, 11296.
6 (a) J. Panteleev, R. Y. Huang, E. K. Lui and M. Lautens, Org. Lett.,
2011, 13, 5314; (b) N. Kim, K. S. Kim, A. K. Gupta and C. H. Oh,
Chem. Commun., 2004, 618; (c) A. Arcadi, M. Aschi, M. Chiarini,
G. Ferrara and F. Marinelli, Adv. Synth. Catal., 2010, 352, 493.
7 M. Lautens and M. Yoshida, J. Org. Chem., 2003, 68, 762.
8 Z. Liu, J. Derosa and K. M. Engle, J. Am. Chem. Soc., 2016, 138, 13076.
9 (a) H. Zeng and R. Hua, J. Org. Chem., 2008, 73, 558; (b) C. H. Oh,
H. H. Jung, K. S. Kim and N. Kim, Angew. Chem., Int. Ed., 2003,
42, 829.
10 Few examples with symmetrical alkynes are shown in ref: (a) D. W.
Robbins and J. F. Hartwig, Science, 2011, 333, 1423; and a single
example of propargyl alcohol and amine is given in ref. 5e without
any detailed survey; for anti-carboarylation, without any hydroaryla-
tion study, of internal alkynes, see: (b) X. Zhang, X. Xie and Y. Liu,
Chem. Sci., 2016, 7, 5815; (c) C. Clarke, C. A. I. Pradillos and
H. W. Lam, J. Am. Chem. Soc., 2016, 138, 8068.
vinylnickel intermediate formed after carbonickelation was
immediately trapped by the Michael acceptors without leaving
room for cis–trans isomerization.
Based on all the above investigative experiments, we proposed
a mechanism as shown in Scheme 9. Accordingly, the ArNiLn
complex (formed via addition reductive elimination)10b was
added in a syn fashion to acetylene with an aryl group dropped
at the less hindered terminal carbon (A). A strong co-ordination
was soon evolved with the nearby flanking DG which halted the
cis–trans isomerization. Subsequent protodenickelation with
EtOH released the olefin 3 and the resultant LnNiOEt upon
reaction with second ArB(OH)2 gave back LnNiAr for the next
cycle. In the case of internal alkyne, the addition resulted in a
reverse regioselection due to steric factors and the resultant vinyl
nickel intermediate B underwent cis–trans isomerization. Since
the trans isomer C was immobilized with intramolecular
co-ordination the reverse isomerism to the cis isomer did not
occur. C then underwent a protodenickelation to afford the trans
addition adduct 6.
In conclusion, we revealed for the first time the regio and
stereoselective addition of arylboronic acids to terminal alkynes
with a directing group tether. A wide variety of highly useful
allylic/homoallylic alcohols, allyl/homoallyl amines and ortho-
alkenyl aniline & phenols in both unprotected and protected
forms were smoothly accessed. Adding all the possible value
addition to the core discovery, a thorough investigative search
of the mechanism led us to unveil the pathways for all di-,
tri- and tetra-substituted olefins.
11 W. Kong, C. Che, J. Wu, L. Ma and G. Zhu, J. Org. Chem., 2014,
79, 5799.
12 Y. A. Jawaheri and M. C. Kimber, Org. Lett., 2016, 18, 3502.
13 (a) R. Kumar, S. H. Thorat and M. S. Reddy, Chem. Commun., 2016,
52, 13475; (b) M. Rajesh, S. Puri, R. Kant and M. S. Reddy, Org. Lett.,
2016, 18, 4332; (c) G. R. Kumar, Y. K. Kumar and M. S. Reddy, Chem.
Commun., 2016, 52, 6589; (d) M. H. Babu, V. Dwivedi, R. Kant and
M. S. Reddy, Angew. Chem., Int. Ed., 2015, 54, 3783; (e) Y. K. Kumar,
G. R. Kumar, T. J. Reddy, B. Sridhar and M. S. Reddy, Org. Lett., 2015,
17, 2226; ( f ) V. Dwivedi, M. H. Babu, R. Kant and M. S. Reddy, Chem.
Commun., 2015, 51, 14996; (g) Y. K. Kumar, G. R. Kumar and
M. S. Reddy, J. Org. Chem., 2014, 79, 823; (h) S. Puri, N. Thirupathi
and M. S. Reddy, Org. Lett., 2014, 16, 5246; (i) M. S. Reddy,
N. Thirupathi, M. H. Babu and S. Puri, J. Org. Chem., 2013, 78, 5878.
14 (a) S. W. Youn, T. Y. Ko, M. J. Jang and S. S. Jang, Adv. Synth. Catal.,
2015, 357, 227; (b) Y. Ho and S. Youn, Org. Lett., 2014, 16, 3720.
Chem. Commun.
This journal is ©The Royal Society of Chemistry 2017