Skip to content
Publicly Available Published by De Gruyter June 8, 2012

Catalytic enantioselective transformations of borylated substrates: Preparation and synthetic applications of chiral alkylboronates

  • Dennis G. Hall , Jack C. H. Lee and Jinyue Ding

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).10.1002/anie.200700975Search 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

Online erschienen: 2012-6-8
Erschienen im Druck: 2012-6-8

© 2013 Walter de Gruyter GmbH, Berlin/Boston

Downloaded on 1.6.2023 from https://www.degruyter.com/document/doi/10.1351/PAC-CON-12-02-04/html
Scroll to top button