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The Inner-Sphere Process in the Enantioselective Tsuji Allylation Reaction with (S)-t-Bu-phosphinooxazoline Ligands

Keith, John A. and Behenna, Douglas C. and Mohr, Justin T. and Ma, Sandy and Marinescu, Smaranda C. and Oxgaard, Jonas and Stoltz, Brian M. and Goddard, William A., III (2007) The Inner-Sphere Process in the Enantioselective Tsuji Allylation Reaction with (S)-t-Bu-phosphinooxazoline Ligands. Journal of the American Chemical Society, 129 (39). pp. 11876-11877. ISSN 0002-7863. doi:10.1021/ja070516j.

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We propose an inner-sphere mechanism explaining the unique performance of the Tsuji asymmetrical allylation reaction using hard prochiral enolate nucleophiles and non-prochiral allyl groups. Using first principles quantum mechanics (B3LYP density functional theory), we find that the pathway for this reaction involves nucleophilic attack followed by interconversion from a five-coordinate Pd complex to a four-coordinate complex. This intermediate is trapped in a potential well and escapes via reductive elimination that proceeds through a seven-membered transition state to generate the product and a Pd^0 complex. This seven-membered transition state contrasts dramatically from the usual three-centered C−C reductive elimination paradigm generally associated with C−C coupling reactions. This inner-sphere asymmetric allylation pathway involving hard enolates is energetically more favorable than outer-sphere nucleophilic attack, a process understood to occur in asymmetric allylic alkylations with soft enolates.

Item Type:Article
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URLURL TypeDescription ItemSupporting Information
Keith, John A.0000-0002-6583-6322
Mohr, Justin T.0000-0002-7005-3322
Marinescu, Smaranda C.0000-0003-2106-8971
Stoltz, Brian M.0000-0001-9837-1528
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2007 American Chemical Society. Received 26 January 2007. Published online 8 September 2007. Published in print 1 October 2007. We thank K. Tani, A. Harned, J. Enquist, and N. Sherden for experimental collaboration and discussion, and M. Day and L. Henling for crystallography assistance. J.A.K. thanks R. (Smith) Nielsen for discussions. This research was partly funded by Chevron-Texaco, and the facilities used were funded by grants from ARO-DURIP, ONR-DURIP, IBM-SUR, Fannie and John Hertz Foundation (D.C.B.), and Eli Lilly (J.T.M.) with additional support from NSF (CTS-0608889, WAG) and NIH-NIGMS (R01GM080269-01, BMS).
Funding AgencyGrant Number
Army Research Office (ARO)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Issue or Number:39
Record Number:CaltechAUTHORS:20170222-080249889
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Official Citation:The Inner-Sphere Process in the Enantioselective Tsuji Allylation Reaction with (S)-t-Bu-phosphinooxazoline Ligands John A. Keith, Douglas C. Behenna, Justin T. Mohr, Sandy Ma, Smaranda C. Marinescu, Jonas Oxgaard, Brian M. Stoltz, and William A. Goddard, III Journal of the American Chemical Society 2007 129 (39), 11876-11877 DOI: 10.1021/ja070516j
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74449
Deposited By: Ruth Sustaita
Deposited On:22 Feb 2017 19:45
Last Modified:11 Nov 2021 05:27

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