Highly Regio‐ and Enantioselective Copper‐Catalyzed Hydroboration of Styrenes
2009; Wiley; Volume: 48; Issue: 33 Linguagem: Inglês
10.1002/anie.200902015
ISSN1521-3773
AutoresDongwan Noh, Heesung Chea, Junghwan Ju, Jaesook Yun,
Tópico(s)Asymmetric Synthesis and Catalysis
ResumoAngewandte Chemie International EditionVolume 48, Issue 33 p. 6062-6064 Communication Highly Regio- and Enantioselective Copper-Catalyzed Hydroboration of Styrenes† Correction(s) for this article Highly Regio- and Enantioselective Copper-Catalyzed Hydroboration of Styrenes Dongwan Noh, Heesung Chea, Junghwan Ju, Jaesook Yun Prof., Volume 48Issue 38Angewandte Chemie International Edition pages: 6938-6938 First Published online: September 1, 2009 Dongwan Noh, Dongwan Noh Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorHeesung Chea, Heesung Chea Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorJunghwan Ju, Junghwan Ju Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorJaesook Yun Prof., Jaesook Yun Prof. [email protected] Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this author Dongwan Noh, Dongwan Noh Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorHeesung Chea, Heesung Chea Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorJunghwan Ju, Junghwan Ju Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this authorJaesook Yun Prof., Jaesook Yun Prof. [email protected] Department of Chemistry and Institute of Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea), Fax: (+82) 31-290-7075Search for more papers by this author First published: 29 July 2009 https://doi.org/10.1002/anie.200902015Citations: 263 † This research was supported by a Korea Science and Engineering Foundation (KOSEF) grant funded by the Korean government (MEST; No. R01-2008-000-20332-0). Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract An existing challenge is the development of efficient regioselective catalytic systems that are compatible with stable hydroboration reagents and can be rendered enantioselective by the use of nonracemic ligands. Copper(I) complexes with chelating phosphines catalyzed the regio- and enantioselective hydroboration of styrenes with pinacolborane (PinBH) at room temperature to afford the corresponding branched boronate esters (see example). Supporting Information Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description anie_200902015_sm_miscellaneous_information.pdf70.2 KB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1For reviews, see: 1aK. Burgess, M. J. Ohlmeyer, Chem. Rev. 1991, 91, 1179–1191; 1bC. M. Crudden, D. Edwards, Eur. J. Org. Chem. 2003, 4695–4712. 2 2aD. S. Matteson, Chem. Rev. 1989, 89, 1535–1551; 2bE. Hupe, I. Marek, P. Knochel, Org. Lett. 2002, 4, 2861–2863; 2cD. Imao, B. W. Glasspoole, V. S. Laberge, C. M. Crudden, J. Am. Chem. Soc. 2009, 131, 5024–5025. 3aK. Burgess, M. Jaspars, Organometallics 1993, 12, 4197–4200; 3bS. Pereira, M. Srebnik, Tetrahedron Lett. 1996, 37, 3283–3286; 3cD. A. Evans, A. R. Muci, R. Stürmer, J. Org. Chem. 1993, 58, 5307–5309; 3dK. N. Harrison, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 9220–9221. 4For a review of rhodium-catalyzed enantioselective hydroboration, see: 4aA.-M. Carroll, T. P. O’Sullivan, P. J. Guiry, Adv. Synth. Catal. 2005, 347, 609–631; 4bT. Hayashi, Y. Matsumoto, Y. Ito, Tetrahedron: Asymmetry 1991, 2, 601–612. 5Rhodium-catalyzed asymmetric hydroboration reactions with pinacolborane resulted in dehydrogenative borylation or only moderate regioselectivity (20–30 % β-borylation): 5aM. Murata, S. Watanabe, Y. Masuda, Tetrahedron Lett. 1999, 40, 2585–2588; 5bC. M. Crudden, Y. B. Hleba, A. C. Chen, J. Am. Chem. Soc. 2004, 126, 9200–9201; 5cS. A. Moteki, D. Wu, K. L. Chandra, D. S. Reddy, J. M. Takacs, Org. Lett. 2006, 8, 3097–3100; for recent examples of rhodium-catalyzed regioselective hydroboration with pinacolborane, see: 5dK. Endo, M. Hirokami, K. Takeuchi, T. Shibata, Synlett 2008, 3231–3233; 5eK. Endo, M. Hirokami, T. Shibata, Organometallics 2008, 27, 5390–5393; see also Ref. [5b]. 6 6aD. Lee, D. Kim, J. Yun, Angew. Chem. 2006, 118, 2851–2853; Angew. Chem. Int. Ed. 2006, 45, 2785–2787; 6bD. Lee, Y. Yang, J. Yun, Org. Lett. 2007, 9, 2749–2751. 7 7aS. Mun, J.-E. Lee, J. Yun, Org. Lett. 2006, 8, 4887–4889; 7bJ.-E. Lee, J. Yun, Angew. Chem. 2008, 120, 151–153; Angew. Chem. Int. Ed. 2008, 47, 145–147; 7cJ.-E. Lee, J. Kwon, J. Yun, Chem. Commun. 2008, 733–734; 7dH.-S. Sim, X. Feng, J. Yun, Chem. Eur. J. 2009, 15, 1939–1943. 8For the in situ generation of CuH from CuOAc with pinacolborane in reductive aldol reactions, see: 8aD. Zhao, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 14440–14441; 8bY. Du, L.-W. Xu, Y. Shimizu, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2008, 130, 16146–16147. 9L. Dang, Z. Lin, T. B. Marder, Organometallics 2008, 27, 4443–4454. 10For the transmetalation of C(sp2)Cu with Sn, see: 10aL. T. Leung, K. S. Leung, P. Chiu, Org. Lett. 2005, 7, 5249–5252; for the transmetalation of C(sp2)Cu with boron, see: 10bB. H. Lipshutz, Ž. V. Boškovič, D. H. Aue, Angew. Chem. 2008, 120, 10337–10340; Angew. Chem. Int. Ed. 2008, 47, 10183–10186; for transmetalation from a copper enolate to a boron enolate with pinacolborane, see Ref. [8a,b]. 11For examples of isolated benzylic organocopper complexes, see: 11aV. W.-W. Yam, W.-K. Lee, K. K. Cheung, H.-K. Lee, W.-P. Leung, J. Chem. Soc. Dalton Trans. 1996, 2889–2891; 11bD. S. Laitar, E. Y. Tsui, J. P. Sadighi, Organometallics 2006, 25, 2405–2408. 12For the thermal stability of alkyl copper(I) complexes coordinated with tertiary phosphines and the decomposition of these complexes through β-elimination, see: A. Miyashita, T. Yamamoto, A. Yamamoto, Bull. Chem. Soc. Jpn. 1977, 50, 1109–1117; see also Refs. [11b, 14]. 13Low conversion was observed with the ligands 1,3-bis(diphenylphosphanyl)propane (dppp), bis[(2-diphenylphosphanyl)phenyl] ether (dpephos), and PPh3. 14An NHC–copper-catalyzed hydroboration of styrene with catecholborane has been reported. Incomplete conversion (73–95 %) and low regioselectivity (α/β 1:2.3–7.3) in favor of the linear isomer were observed: V. Lillo, M. R. Fructos, J. Ramírez, A. A. C. Braga, F. Maseras, M. M. Díaz-Requejo, P. J. Pérez, E. Fernández, Chem. Eur. J. 2007, 13, 2614–2621. 15L. Dang, H. Zhao, Z. Lin, T. B. Marder, Orgnometallics 2007, 26, 2824–2832. 16In most cases of the enantioselective catalysis of CuH addition reactions, the stereocenter is generated at the position at which H− is added, and not at the position at which the Cu atom is located in the organocopper intermediate; for a review, see: C. Deutsch, N. Krause, B. H. Lipshutz, Chem. Rev. 2008, 108, 2916–2927. 17We found that Z alkenes, such as (Z)-β-methylstyrene and indene, were not reactive. 18We observed 63 % conversion of 1 h in 24 h at 40 °C. 19Compounds 2 j and 2 k were obtained with 66 and 78 % ee, respectively. Citing Literature Volume48, Issue33August 3, 2009Pages 6062-6064 ReferencesRelatedInformation
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