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a pioneering work of copperꢀmediated
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borylalkylation of activated alkynes, see: (f) Okuno, Y.; Yamashita, M.;
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(7) For other examples for catalyzed regioꢀ and stereoselective syntheꢀ
sis of tetrasubstituted alkenylboronates, see: (1) Itami, K.; Kamei, T.;
Yoshida, J.ꢀI. J. Am. Chem. Soc. 2003, 125, 14670. (b) Shimizu, M.; Nakꢀ
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(8) (a) Nishihara, Y.; Okada, Y.; Jiao, J. Suetsugu, M.; Lan, M.ꢀT.; Kiꢀ
noshita, M.; Iwasaki, M.; Takagi, K. Angew. Chem. Int. Ed. 2011, 50,
8660. For the related stereoselective synthesis of tetrasubstituted alkenylꢀ
boronates containing aromatic substituents, see: (b) Nishihara, Y.;
Miyasaka, M.; Okamoto, M.; Takahashi, H.; Inoue, E.; Tanemura, K.;
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(9) For another nonꢀcatalytic method, see: Endo, K.; Hirokami, M.;
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(10) For selected examples of regioselective addition to electronically
unbiased internal alkynes, see: (a) Malik, H. A.; Sormunen, G. J.; Montꢀ
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(14) Consistent with this explanation, regioselectivity decreased acꢀ
cording to the decreased steric demand of boronates. When less bulky
bis[(ꢀ)ꢀpinanediolato]diboron and bis(hexylene glycolato)diboron were
used instead of (Bpin)2, regioselectivity decreased to 5.9 : 1 and 1 : 1.5,
respectively, using a NQIMesCuCl catalyst (cf. 10 : 1 with (Bpin)2, see
Table 1, entry 8).
(15) πꢀAccepting NHCꢀ and cyclic (alkyl)(amino)carbene (CAAC)ꢀ
gold catalysts promoting addition reactions to alkenes and alkynes were
reported. See: (a) LópezꢀGómez, M. J.; Martin, D.; Bertrand, G. Chem.
Commun. 2013, 49, 4483. (b) Hu, X.; Martin, D.; Malaimi, M.; Bertrand,
G. J. Am. Chem. Soc. 2014, 136, 13594. (c) Lavallo, V.; Frey, G. D.;
Donnadieu, B.; Soleilhavoup, M.; Bertrand, G. Angew. Chem. Int. Ed.
2008, 47, 5224. (d) Kinjo, R.; Donnadieu, B.; Bertrand, G. Angew. Chem.
Int. Ed. 2011, 50, 5560. (e) Alcarazo, M.; Stork, T.; Anoop, A.; Thiel, W.;
Fürstner, A. Angew. Chem. Int. Ed. 2010, 49, 2542.
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(16) The use of NQIMesCuCl in organic synthesis is unprecedented. A
NQIMesꢀnickel complex was used in Kumada coupling reaction. See: (a)
Sanderson, M. D.; Kamplain, J. W.; Bielawski, C. W. J. Am. Chem. Soc.
2006, 128, 16514. (b) Tennyson, A. G.; Lynch, V. M.; Bielawski, C. W. J.
Am. Chem. Soc. 2010, 132, 9420.
(17) In contrast, the ironꢀcatalyzed alkylboration provided a ringꢀ
opening product. See ref 3.
(18) For a review of stereoselective synthesis of tetrasubstituted alꢀ
kenes, see: Flynn, A. B.; Ogilvie, W. W. Chem. Rev. 2007, 107, 4698.
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