ChemComm
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COMMUNICATION
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For a related report on Cu(I)-catalysed desymmetrisation via a two-step 20 One possible explanation for this is that tautomerisation of the desired
conjugate addition/oxidation method, see: (a) K. Aikawa, T. Okamoto
and K. Mikami, J. Am. Chem. Soc., 2012, 134, 10329; For direct
vinylogous nucleophilic addition of deconjugated butenolides using
oxidative Heck product can now occur, allowing 1,2-addition (see ref.
produce the triarylated product 5an.
DOI: 10.1039/C5CC00407A
organocatalysts, see: (b) M. S. Manna and S. Mukherjee, Chem. Sci., 21 T. Yamamoto, T. Ohta and Y. Ito, Org. Lett., 2005, 7, 4153.
2014, 5, 1627. 22 Y. Kayaki, T. Koda and T. Ikariya, Eur. J. Org. Chem., 2004, 4989.
For review on desymmetrising cyclopentanes, see: M. S. Manna and S. 23 It should be noted that commercial aryl boronic acid samples are
7
8
Mukherjee, Org. Biomol. Chem., 2015, 13, 18.
often a mixture of the aryl boronic acid and arylboroxine in
equilibrium. D. G. Hall, in Boronic Acids, Wiley-VCH Verlag GmbH
& Co. KGaA, 2011, pp. 1-133.
For recent reviews on asymmetric Heck and related reactions, see: (a) D.
McCartney and P. J. Guiry, Chem. Soc. Rev., 2011, 40, 5122; (b) M.
Oestreich, Angew. Chem. Int. Ed., 2014, 53, 2282; (c) H. Li, C. H. Ding, 24 Alternatively, arylboronic acid pinacol esters can also be used, although
B. Xu and X. L. Hou, Acta Chim. Sinica, 2014, 72, 765.
See ESI for details on substrate synthesis.
10 For selected examples of intermolecular enantioselective oxidative Heck
the yields are slightly lower than with arylboronic acids. For example,
2bh is formed in 84% and 78% yields using phenylboronic acid and
pinacol ester respectively, under general conditions shown in Table 2.
9
reactions, see: (a) T.-S. Mei, H. H. Patel and M. S. Sigman, Nature, 25 H. Shimizu, J. C. Holder and B. M. Stoltz, Beilstein J. Org. Chem., 2013,
2014, 508, 340; (b) T.-S. Mei, E. W. Werner, A. J. Burckle and M. S. 9, 1637.
Sigman, J. Am. Chem. Soc., 2013, 135, 6830; (c) S. Sakaguchi, K. S. 26 E. W. Werner, T.-S. Mei, A. J. Burckle and M. S. Sigman, Science,
Yoo, J. O'Neill, J. H. Lee, T. Stewart and K. W. Jung, Angew. Chem. Int. 2012, 338, 1455.
Ed., 2008, 47, 9326; (d) K. S. Yoo, C. P. Park, C. H. Yoon, S. 27 R. Díaz-Torres and S. Alvarez, Dalton Trans., 2011, 40, 10742.
Sakaguchi, J. O'Neill and K. W. Jung, Org. Lett., 2007, 9, 3933.
11 For reviews of catalytic enantioselective desymmetrisations, see: (a) K.
Mikami and A. Yoshida, J. Synth. Org. Chem. Jpn., 2002, 60, 732; (b) T.
Rovis, in New Frontiers in Asymmetric Catalysis, eds. K. Mikami and
M. Lautens, Wiley: Hoboken, NJ, 2007, p. 275; (c) R. S. Ward, Chem.
Soc. Rev., 1990, 19, 1; (d) M. C. Willis, J. Chem. Soc. Perkin Trans. 1,
1999, 1765.
28 The arylboronic acid pinacol ester 7n was used here as it is commercially
available while the corresponding arylboronic acid is not.
12 Quaternary Stereocenters: Challenges and Solutions for Organic
Synthesis, Blackwell Science Publ, Oxford, 2005.
13 M. S. Manna and S. Mukherjee, J. Am. Chem. Soc., 2015, 137, 130.
14 (a) D. Tanaka and A. G. Myers, Org. Lett., 2004, 6, 433; (b) Y. Fall, H.
Doucet and M. Santelli, Tetrahedron, 2009, 65, 489.
15 For reviews on oxidative Heck, see: (a) B. Karimi, H. Behzadnia, D.
Elhamifar, P. F. Akhavan, F. K. Esfahani and A. Zamani, Synthesis,
2010, 1399; (b) Y. J. Su and N. Jiao, Curr. Org. Chem., 2011, 15, 3362.
16 Selected papers on oxidative Heck, for examples on cyclic enones see
ref. 17-18: (a) M. M. S. Andappan, P. Nilsson and M. Larhed, Chem.
Commun., 2004, 218; (b) C. S. Cho and S. Uemura, J. Organomet.
Chem., 1994, 465, 85; (c) J. D. Crowley, K. D. Hanni, A.-L. Lee and D.
A. Leigh, J. Am. Chem. Soc., 2007, 129, 12092; (d) J. H. Delcamp, A. P.
Brucks and M. C. White, J. Am. Chem. Soc., 2008, 130, 11270; (e) J. H.
Delcamp, P. E. Gormisky and M. C. White, J. Am. Chem. Soc., 2013,
135, 8460; (f) X. Du, M. Suguro, K. Hirabayashi, A. Mori, T. Nishikata,
N. Hagiwara, K. Kawata, T. Okeda, H. F. Wang, K. Fugami and M.
Kosugi, Org. Lett., 2001, 3, 3313; (g) Z. He, S. Kirchberg, R. Froehlich
and A. Studer, Angew. Chem. Int. Ed., 2012, 51, 3699; (h) A. Inoue, H.
Shinokubo and K. Oshima, J. Am. Chem. Soc., 2003, 125, 1484; (i) Y. C.
Jung, R. K. Mishra, C. H. Yoon and K. W. Jung, Org. Lett., 2003, 5,
2231; (j) L. Meng, C. Liu, W. Zhang, C. Zhou and A. Lei, Chem.
Commun., 2014, 50, 1110; (k) J. Ruan, X. Li, O. Saidi and J. Xiao, J.
Am. Chem. Soc., 2008, 130, 2424; (l) Y. Su and N. Jiao, Org. Lett., 2009,
11, 2980; (m) P. Sun, Y. Zhu, H. Yang, H. Yan, L. Lu, X. Zhang and J.
Mao, Org. Biomol. Chem., 2012, 10, 4512; (n) E. W. Werner and M. S.
Sigman, J. Am. Chem. Soc., 2010, 132, 13981; (o) C. Zheng, D. Wang
and S. S. Stahl, J. Am. Chem. Soc., 2012, 134, 16496.
17 K. S. Yoo, C. H. Yoon and K. W. Jung, J. Am. Chem. Soc., 2006, 128,
16384.
18 For example, see: (a) S. E. Walker, J. A. Jordan-Hore, D. G. Johnson, S.
A. Macgregor and A.-L. Lee, Angew. Chem. Int. Ed., 2014, 53, 13876;
(b) Y. W. Kim and G. I. Georg, Org. Lett., 2014, 16, 1574; (c) A. Carrër,
J.-D. Brion, S. Messaoudi and M. Alami, Org. Lett., 2013, 15, 5606; (d)
A. L. Gottumukkala, J. F. Teichert, D. Heijnen, N. Eisink, S. van Dijk,
C. Ferrer, A. van den Hoogenband and A. J. Minnaard, J. Org. Chem.,
2011, 76, 3498; (e) Y. Izawa, C. Zheng and S. S. Stahl, Angew. Chem.
Int. Ed., 2013, 52, 3672; (f) Y. Li, Z. Qi, H. Wang, X. Fu and C. Duan, J.
Org. Chem., 2012, 77, 2053; (g) B. Mondal, S. Hazra and B. Roy,
Tetrahedron Lett., 2014, 55, 1077; (h) D.-C. Xiong, L.-H. Zhang and
X.-S. Ye, Org. Lett., 2009, 11, 1709; (i) K. S. Yoo, J. O'Neill, S.
Sakaguchi, R. Giles, J. H. Lee and K. W. Jung, J. Org. Chem., 2010, 75,
95; (j) J. A. Jordan-Hore, J. N. Sanderson and A.-L. Lee, Org. Lett.,
2012, 14, 2508; (k) S. E. Walker, J. Boehnke, P. E. Glen, S. Levey, L.
Patrick, J. A. Jordan-Hore and A.-L. Lee, Org. Lett., 2013, 15, 1886. See
also ref.16a and 17.
19 K. M. Gligorich and M. S. Sigman, Chem. Commun., 2009, 3854.
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