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The Origins of Enantioselectivity in Rh–Diene Complex Catalysed Arylation of Cyclohex‐2‐enones

2011; Wiley; Volume: 18; Issue: 1 Linguagem: Inglês

10.1002/chem.201102421

ISSN

1521-3765

Autores

S. Gosiewska, Jevgenij A. Raskatov, Ryo Shintani, Tamio Hayashi, John M. Brown,

Tópico(s)

Chemical synthesis and alkaloids

Resumo

Chemistry – A European JournalVolume 18, Issue 1 p. 80-84 Communication The Origins of Enantioselectivity in Rh–Diene Complex Catalysed Arylation of Cyclohex-2-enones Dr. Silvia Gosiewska, Dr. Silvia Gosiewska Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. Jevgenij A. Raskatov, Dr. Jevgenij A. Raskatov Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. Ryo Shintani, Dr. Ryo Shintani Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988Search for more papers by this authorProf. Tamio Hayashi, Corresponding Author Prof. Tamio Hayashi [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 Tamio Hayashi, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 John M. Brown, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. John M. Brown, Corresponding Author Dr. John M. Brown [email protected] Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644 Tamio Hayashi, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 John M. Brown, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this author Dr. Silvia Gosiewska, Dr. Silvia Gosiewska Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. Jevgenij A. Raskatov, Dr. Jevgenij A. Raskatov Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. Ryo Shintani, Dr. Ryo Shintani Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988Search for more papers by this authorProf. Tamio Hayashi, Corresponding Author Prof. Tamio Hayashi [email protected] Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 Tamio Hayashi, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 John M. Brown, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this authorDr. John M. Brown, Corresponding Author Dr. John M. Brown [email protected] Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644 Tamio Hayashi, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988 John M. Brown, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644Search for more papers by this author First published: 12 December 2011 https://doi.org/10.1002/chem.201102421Citations: 46Read 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 Graphical Abstract Chiral diene ligands: Conjugate addition of aryl boronic acids to cyclohexenone is catalysed by Rh complexes of the simple chiral diene (S)-bicyclo[3.3.1]nona-2,6-diene in unexpectedly high ee. Insight into the reasons, and more generally the TS structure and pathways with other catalysts, was explored by using density functional theory. There was a gratifyingly good agreement between calculation and experiment. A lack of obvious steric discrimination together with systematic variations in TS structure implicated stereoelectronics. References 1 1aT. Hayashi, K. Ueyama, N. Tokunaga, K. Yoshida, J. Am. Chem. Soc. 2003, 125, 11508– 11509; 1bC. Fischer, C. Defieber, T. Suzuki, E. M. Carreira, J. Am. Chem. Soc. 2004, 126, 1628– 1629. 2 2aC. Defieber, H. Grutzmacher, E. M. Carreira, Angew. Chem. 2008, 120, 4558– 4579; Angew. Chem. Int. Ed. 2008, 47, 4482– 4502; 2bR. Shintani, T. Hayashi, Aldrichimica Acta 2009, 42, 31– 38. 3H. J. Edwards, J. D. 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Chem. 2011, 76, 4905– 4909. 18The preferred conformation observed here (C5-endo to the metal) is seen in the one monometallic cyclohex-2-enone complex in the CSSR database: M. Morita, K. Inoue, T. Yoshida, S. Ogoshi, H. Kurosawa, J. Organomet. Chem. 2004, 689, 894– 898. 19For alkene bonding distortions vis-à-vis the Chatt–Dewar–Duncanson model, see: D. W. Price, M. G. B. Drew, K. K. Hii, J. M. Brown, Chem. Eur. J. 2000, 6, 4587– 4596. 20Note the change in CIP priorities in the [3.3.1] series. (R,R)-1 b and (S,S)-2 b both prefer (R)-product in accord with Figure 2. 21aO. A. Wong, B. Wang, M. X. Zhao, Y. Shi, J. Org. Chem. 2009, 74, 6335– 6338, and earlier papers; 21bD. Seebach, A. K. Beck, D. M. Badine, M. Limbach, A. Eschenmoser, A. M. Treasurywala, R. Hobi, W. Prikoszovich, B. Linder, Helv. Chim. Acta 2007, 90, 425– 471; 21cfor a review of purely electronic effects in asymmetric catalysis see: S. P. Flanagan, P. J. Guiry, J. Organomet. Chem. 2006, 691, 2125– 2154. 22Stereoelectronics is defined in the IUPAC Gold Book: Pertaining to the dependence of the properties (especially the energy) of a molecular entity in a particular electronic state (or of a transition state) on relative nuclear geometry. 23 23aH. Urtel, C. Meier, F. Rominger, P. Hofmann, Organometallics 2010, 29, 5496– 5503; 23bS. T. H. Willems, J. C. Russcher, P. H. M. Budzelaar, B. de Bruin, R. de Gelder, J. M. M. Smits, A. W. Gal, Chem. Commun. 2002, 148– 149; 23cJ. M. Brown, P. J. Guiry, D. W. Price, M. B. Hursthouse, S. Karalulov, Tetrahedron: Asymmetry 1994, 5, 561– 564. 24Computation was conducted with the Gaussian03 program suite: Revision B.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. 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Citing Literature 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 chem_201102421_sm_miscellaneous_information.pdf12.2 MB 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. Volume18, Issue1January 2, 2012Pages 80-84 ReferencesRelatedInformation

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