Organoboronic acid derivatives are well-established intermediates for the preparation of alcohols and amines, and in the formation of C–C bonds via different reactions, including homologations, carbonyl allylboration, or transition-metal-catalyzed cross-coupling chemistry. In the past decade, there has been great interest in the development of catalytic enantioselective methods for the preparation of chiral, optically enriched organoboronates as precursors of enantioenriched compounds. While the mainstream strategy remains the late-stage borylation of organic functional groups, our group has focused on an alternate strategy focused on modification of boron-containing substrates. In this way, acyclic and cyclic secondary alkyl- and allyl-boronates were prepared through catalytic enantioselective processes such as [4 + 2] cycloadditions, isomerizations, allylic substitutions, and conjugate additions. The resulting optically enriched boronates have been successfully utilized in the syntheses of complex natural products and drugs. One remaining challenge in the chemistry of secondary alkylboronate derivatives is their cross-coupling, especially with control of stereoselectivity. In this regard, our recent approach featured the conjugate asymmetric borylation of β-boronyl acrylates, providing the first enantioselective preparation of highly optically enriched 1,1-diboronyl derivatives. The chirality of these geminal diboron compounds is conferred through the use of two distinct boronate adducts, which can be coupled chemo- and stereoselectively with a variety of aryl and alkenyl halides under palladium catalysis.
Conference
International Meeting on Boron Chemistry (IMEBORON-XIV), International Symposium on Boron Chemistry, IMEB, Boron Chemistry, 14th, Niagara Falls, Canada, 2011-09-11–2011-09-15
References
1 D. G. Hall (Ed.). Boronic Acids, 2nd ed., Wiley-VCH, Weinheim (2001).Search in Google Scholar
2a 10.1021/cr00039a007, N. Miyaura, A. Suzuki. Chem. Rev.95, 2457 (1995).Search in Google Scholar
2b F. Bellina, A. Carpita, R. Rossi. Synthesis15, 2419 (2004).10.1055/s-2004-831223Search in Google Scholar
3a 10.1021/ja00318a040, H. C. Brown, B. Singaram. J. Am. Chem. Soc.106, 1797 (1984).Search in Google Scholar
3b 10.1021/ar00152a001, H. C. Brown, B. Singaram. Acc. Chem. Res.21, 287 (1988).Search in Google Scholar
4 10.1016/S0040-4020(98)00321-4, D. S. Matteson. Tetrahedron54, 10555 (1988).Search in Google Scholar
5 Recent selected examples.Search in Google Scholar
5a 10.1021/ja8094075, D. Imao, B. W. Glasspoole, V. S. Laberge, C. M. Crudden. J. Am. Chem. Soc.131, 5024 (2009).Search in Google Scholar PubMed
5b 10.1002/tcr.20168, S. P. Thomas, R. M. French, V. Jheengut, V. K. Aggarwal. Chem. Rec.9, 24 (2009).Search in Google Scholar PubMed
5c 10.1002/anie.200901900, A. Ros, V. K. Aggarwal. Angew. Chem., Int. Ed.48, 6289 (2009).Search in Google Scholar PubMed
5d 10.1002/anie.200901194, G. Dutheuil, M. P. Webster, P. A. Worthington, V. K. Aggarwal. Angew. Chem., Int. Ed.48, 6317 (2009).Search in Google Scholar PubMed
5e 10.1002/anie.200805604, S. P. Thomas, V. K. Aggarwal. Angew. Chem., Int. Ed.48, 1896 (2009).Search in Google Scholar PubMed
5f 10.1002/anie.200805272, F. Schmidt, F. Keller, E. Vedrenne, V. K. Aggarwal. Angew. Chem., Int. Ed.48, 1149 (2009).Search in Google Scholar PubMed
5g 10.1002/anie.200902015, D. Noh, H. Chea, J. Ju, J. Yun. Angew. Chem., Int. Ed.48, 6062 (2009).Search in Google Scholar PubMed
5h 10.1021/ja809382c, Y. Lee, A. H. Hoveyda. J. Am. Chem. Soc.131, 3160 (2009).Search in Google Scholar PubMed PubMed Central
5i 10.1021/ja9047762, T. Kliman, S. N. Mlinarski, J. P. Morken. J. Am. Chem. Soc.131, 13210 (2009).Search in Google Scholar PubMed PubMed Central
5j 10.1021/ja910750b, R. J. Ely, J. P. Morken. J. Am. Chem. Soc.132, 2534 (2010).Search in Google Scholar PubMed PubMed Central
5k 10.1002/anie.201001371, V. Bagutski, R. M. French, V. Aggarwal. Angew. Chem., Int. Ed.49, 5142 (2010).Search in Google Scholar PubMed
5l 10.1021/ja104254d, A. Guzman-Martinez, A. H. Hoveyda. J. Am. Chem. Soc.132, 10630 (2010).Search in Google Scholar PubMed PubMed Central
5m 10.1002/anie.201102398, R. Corberan, N. W. Mszar, A. H. Hoveyda. Angew. Chem., Int. Ed.50, 7079 (2011).Search in Google Scholar PubMed
5n 10.1002/anie.201102404, C. H. Schuster, B. Li, J. P. Morken. Angew. Chem., Int. Ed.50, 7906 (2011).Search in Google Scholar PubMed PubMed Central
5o 10.1002/chem.201102581, H. K. Scott, V. K. Aggarwal. Chem.—Eur. J.17, 13124 (2011).Search in Google Scholar PubMed
6 10.1016/S0022-328X(01)01239-6, M. Ueda, A. Saitoh, N. Miyaura. J. Organomet. Chem.642, 145 (2002).Search in Google Scholar
7a 10.1021/ja036368o, X. Gao, D. G. Hall. J. Am. Chem. Soc.125, 9308 (2003).Search in Google Scholar
7b 10.1002/chem.200501197, X. Gao, D. G. Hall, M. Deligny, A. Favre, F. Carreaux, B. Carboni. Chem.—Eur. J.13, 3132 (2006).Search in Google Scholar
8 10.1021/ja042827p, X. Gao, D. G. Hall. J. Am. Chem. Soc.127, 1628 (2005).Search in Google Scholar
9 10.1021/ja906429c, M. N. Penner, V. Rauniyar, L. Kaspar, D. G. Hall. J. Am. Chem. Soc.131, 14216 (2009).Search in Google Scholar
10 10.1055/s-2000-6274, M. Murata, T. Oyama, S. Watanabe, Y. Masuda. Synthesis6, 778 (2000).Search in Google Scholar
11 10.1021/ja903946f, S. Lessard, F. Peng, D. G. Hall. J. Am. Chem. Soc.131, 9612 (2009).Search in Google Scholar
12a 10.1351/pac198860010123, R. W. Hoffmann. Pure Appl. Chem.60, 123 (1988).Search in Google Scholar
12b 10.1351/pac199062101993, R. W. Hoffmann, G. Neil, A. Schlapbach. Pure Appl. Chem.62, 1993 (1990).Search in Google Scholar
13 10.1016/S0022-328X(00)89998-2, R. W. Hoffmann, U. Weidmann. J. Organomet. Chem.195, 137 (1980).Search in Google Scholar
14 10.1007/978-3-642-15334-1_7, J. F. Hartwig, M. J. Pouy. Top. Organomet. Chem.34, 169 (2011).Search in Google Scholar
15 10.1016/j.tetlet.2007.02.124, F. Peng, D. G. Hall. Tetrahedron Lett.48, 3305 (2007).Search in Google Scholar
16 10.1002/anie.200353744, K. Tissot-Croset, D. Polet, A. Alexakis. Angew. Chem., Int. Ed.43, 2426 (2004).Search in Google Scholar PubMed
17 L. Carosi, D. G. Hall. Angew. Chem., Int. Engl.46, 5913 (2007).Search in Google Scholar
18a 10.1021/ja027453j, J. W. J. Kennedy, D. G. Hall. J. Am. Chem. Soc.124, 11586 (2002).Search in Google Scholar PubMed
18b 10.1021/ja0210345, T. Ishiyama, T-a. Ahiko, N. Miyaura. J. Am. Chem. Soc.124, 12414 (2002).Search in Google Scholar PubMed
18c 10.1055/s-2007-980384, D. G. Hall. Synlett11, 1644 (2007).Search in Google Scholar
18d H. Lachance, D. G. Hall. Organic Reactions, Vol. 73, S. E. Denmark (Ed.), John Wiley, New York (2008).Search in Google Scholar
19 Review.Search in Google Scholar
19a 10.1039/c1cc10528k, E. Hartmann, D. J. Vyas, M. Oestreich. Chem. Commun.47, 7917 (2011); selected examples.Search in Google Scholar PubMed
19b 10.1021/ol061955a, S. Mun, J.-E. Lee, J. Yun. Org. Lett.8, 4887 (2006).Search in Google Scholar PubMed
19c 10.1002/anie.200703699, J.-E. Lee, J. Yun. Angew. Chem., Int. Ed.47, 145 (2008).Search in Google Scholar PubMed
19d 10.1002/chem.200802150, H.-S. Sim, X. Feng, J. Yun. Chem.—Eur. J.15, 1939 (2009).Search in Google Scholar PubMed
19e 10.1002/adsc.200900040, H. Chea, H. Sim, J. Yun. Adv. Synth. Catal.351, 855 (2009).Search in Google Scholar
19f 10.1021/om800946k, V. Lillo, A. Prieto, A. Bonet, M. M. Díaz-Requejo, J. Ramírez, P. J. Pérez, E. Fernández. Organometallics28, 659 (2009).Search in Google Scholar
19g 10.1039/b900741e, W. J. Fleming, H. Müller-Bunz, V. Lillo, E. Fernández, J. Guiry. Org. Biomol. Chem.7, 2520 (2009).Search in Google Scholar PubMed
19h 10.1039/b909341a, V. Lillo, M. J. Geier, S. A. Westcott, E. Fernández. Org. Biomol. Chem.7, 4674 (2009).Search in Google Scholar PubMed
19i 10.1002/anie.201001198, A. Bonet, H. Gulyás, E. Fernández. Angew. Chem., Int. Ed.49, 5130 (2010).Search in Google Scholar PubMed
19j 10.1002/asia.201000826, A. Bonet, C. Solé, H. Gulyás, E. Fernández. Chem.—Asian J.6, 1011 (2011).Search in Google Scholar PubMed
19k 10.1002/adsc.201000842, C. Solé, A. Whiting, H. Gulyás, E. Fernández. Adv. Synth. Catal.353, 376 (2011).Search in Google Scholar
19l 10.1021/ja809382c, Y. Lee, A. H. Hoveyda. J. Am. Chem. Soc.131, 3160 (2009).Search in Google Scholar PubMed PubMed Central
19m 10.1021/ja902889s, K.-S. Lee, A. R. Zhugralin, A. H. Hoveyda. J. Am. Chem. Soc.131, 7253 (2009).Search in Google Scholar PubMed PubMed Central
19n 10.1021/ja9045839, I.-H. Chen, L. Yin, W. Itano, M. Kanai, M. Shibasaki. J. Am. Chem. Soc.131, 11664 (2009).Search in Google Scholar PubMed
19o 10.1021/ol101691p, I.-H. Chen, M. Kanai, M. Shibasaki. Org. Lett.12, 4098 (2010).Search in Google Scholar PubMed
19p 10.1039/b915759j, T. Shiomi, T. Adachi, K. Toribatake, L. Zhou, H. Nishiyama. Chem. Commun.45, 5987 (2009).Search in Google Scholar PubMed
19q 10.1021/ol1021756, J. K. Park, H. H. Lackey, M. D. Rexford, K. Kovnir, M. Shatruk, D. T. McQuade. Org. Lett.12, 5008 (2010).Search in Google Scholar PubMed
19r 10.1039/c0cc02211j, D. Hirsch-Weil, K. A. Abboud, S. Hong. Chem. Commun.46, 7525 (2010).Search in Google Scholar PubMed
20 10.1021/ja9104057, J. C. H. Lee, D. G. Hall. J. Am. Chem. Soc.132, 5544 (2010).Search in Google Scholar PubMed
21 E. P. Gillis, M. D. Burke. Aldrichim. Acta42, 17 (2009).Search in Google Scholar
22 10.1021/ar050199q, G. A. Molander, N. Ellis. Acc. Chem. Res.40, 275 (2007).Search in Google Scholar PubMed
23a 10.1021/ja067975p, H. Noguchi, K. Hojo, M. Suginome. J. Am. Chem. Soc.129, 758 (2007).Search in Google Scholar PubMed
23b 10.1021/ol702420x, H. Noguchi, T. Shioda, C.-M. Chou, M. Suginome. Org. Lett.10, 377 (2008).Search in Google Scholar PubMed
24 10.1021/ja0666046, S.-Y. Wang, S.-J. Ji, T.-P. Loh. J. Am. Chem. Soc.129, 276 (2007).Search in Google Scholar PubMed
25a 10.1021/ja053020f, R. Des Mazery, M. Pullez, F. López, S. R. Harutyunyan, A. J. Minnaard, B. L. Feringa. J. Am. Chem. Soc.127, 9966 (2005).Search in Google Scholar PubMed
25b 10.1021/ja0651862, G. P. Howell, S. P. Fletcher, K. Geurts, B. ter Horst, L. Feringa. J. Am. Chem. Soc.128, 14977 (2006).Search in Google Scholar PubMed
25c 10.1021/ol702425a, B. M. Ruiz, K. Geurts, M. A. Fernández-Ibáñez, B. ter Horst, A. J. Minnaard, B. L. Feringa. Org. Lett.9, 5123 (2007).Search in Google Scholar PubMed
26 10.1021/ja992366l, D. H. Appella, Y. Moritani, R. Shintani, E. M. Ferreira, S. L. Buchwald. J. Am. Chem. Soc.121, 9473 (1999).Search in Google Scholar
27 10.1016/j.tet.2011.07.088, J. Ding, D. G. Hall. Tetrahedron68, 3428 (2012).Search in Google Scholar
28 J. Ding, J. C. H. Lee, D. G. Hall. Manuscript in preparation.Search in Google Scholar
29a 10.1039/b911537d, C. M. Crudden, B. W. Glasspoole, C. J. Lata. Chem. Commun.45, 6704 (2009).Search in Google Scholar PubMed
29b 10.1038/nchem.1210, B. W. Glasspoole, C. M. Crudden. Nat. Chem.3, 912 (2011).Search in Google Scholar PubMed
30 10.1021/ja8094075, D. Imao, B. W. Glasspoole, V. S. Laberge, C. M. Crudden. J. Am. Chem. Soc.131, 5024 (2009).Search in Google Scholar PubMed
31 10.1021/ja106632j, T. Ohmura, T. Awano, M. Suginome. J. Am. Chem. Soc.132, 13191 (2010).Search in Google Scholar PubMed
32 10.1021/ja108949w, D. Sandrock, L. Jean-Gérard, C. Y. Chen, S. D. Dreher, G. A. Molander. J. Am. Chem. Soc.132, 17109 (2010).Search in Google Scholar PubMed PubMed Central
33 10.1021/ja105176v, K. Endo, T. Ohkubo, M. Hirokami, T. Shibata. J. Am. Chem. Soc.132, 11033 (2010).Search in Google Scholar PubMed
34 10.1038/nchem.1150, J. C. H. Lee, R. McDonald, D. G. Hall. Nat. Chem.3, 894 (2011).Search in Google Scholar PubMed
© 2013 Walter de Gruyter GmbH, Berlin/Boston
