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Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts

Avila, Carolina M. and Patel, Jigar S. and Reddi, Yernaidu and Saito, Masato and Nelson, Hosea M. and Shunatona, Hunter P. and Sigman, Matthew S. and Sunoj, Raghavan B. and Toste, F. Dean (2017) Enantioselective Heck-Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts. Angewandte Chemie International Edition, 56 (21). pp. 5806-5811. ISSN 1433-7851. PMCID PMC5528849. doi:10.1002/anie.201702107.

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A mild, asymmetric Heck–Matsuda reaction of five-, six- and seven-membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd⁰ and chiral anion co-catalysts, the latter functioning as a chiral anion phase-transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by-products. More specifically, BINAM-derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP-D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Avila, Carolina M.0000-0003-3334-4347
Reddi, Yernaidu0000-0002-6743-9582
Saito, Masato0000-0001-7908-0776
Nelson, Hosea M.0000-0002-4666-2793
Sigman, Matthew S.0000-0002-5746-8830
Sunoj, Raghavan B.0000-0002-6484-2878
Toste, F. Dean0000-0001-8018-2198
Additional Information:© 2017 Wiley-VCH. Issue Online: 08 May 2017. Version of Record online: 18 April 2017. Manuscript revised: 26 March 2017. Manuscript received: 26 February 2017. We acknowledge the National Institute of General Medical Sciences (R35 GM118190 to F.D.T. and R01 GM063540 to M.S.S.) for partial support of this work and IITB supercomputing for the computing time. C.M.A. thanks Science without Borders for a postdoctoral fellowship (CSF/CNPq 201758/2014-8) and H.M.N. acknowledges the UNCF and Merck for generous funding. We thank S. Kim for the paper revision and helpful discussion and suggestions, Dr. G. Schäfer for helpful suggestions, and Dr. W. Wolf and A. G. DiPasquale for the X-ray structure of 15 b and 19. X-ray crystallography was performed using the UC Berkeley College of Chemistry CheXray facility supported by the NIH Shared Instrumentation Grant S10-RR027172. The authors declare no conflict of interest.
Funding AgencyGrant Number
NIHR35 GM118190
NIHR01 GM063540
Science without BordersCSF/CNPq 201758/2014-8
United Negro College FundUNSPECIFIED
Subject Keywords:chiral anions; Heck–Matsuda reaction; Heck reaction; palladium; phase-transfer catalysis
Issue or Number:21
PubMed Central ID:PMC5528849
Record Number:CaltechAUTHORS:20210811-225352045
Persistent URL:
Official Citation:C. M. Avila, J. S. Patel, Y. Reddi, M. Saito, H. M. Nelson, H. P. Shunatona, M. S. Sigman, R. B. Sunoj, F. D. Toste, Angew. Chem. Int. Ed. 2017, 56, 5806.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110219
Deposited By: George Porter
Deposited On:13 Aug 2021 19:34
Last Modified:13 Aug 2021 19:34

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