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Non-Carbonyl-Stabilized Metallocarbenoids in Synthesis: The Development of a Tandem Rhodium-Catalyzed Bamford−Stevens/Thermal Aliphatic Claisen Rearrangement Sequence

May, Jeremy A. and Stoltz, Brian M. (2002) Non-Carbonyl-Stabilized Metallocarbenoids in Synthesis: The Development of a Tandem Rhodium-Catalyzed Bamford−Stevens/Thermal Aliphatic Claisen Rearrangement Sequence. Journal of the American Chemical Society, 124 (42). pp. 12426-12427. ISSN 0002-7863. doi:10.1021/ja028020j. https://resolver.caltech.edu/CaltechAUTHORS:20170215-150235551

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Abstract

A tandem rhodium-catalyzed Bamford−Stevens/Claisen rearrangement is presented. The tandem reaction uses Eschenmoser hydrazones for the in situ generation of non-carbonyl-stabilized diazo alkanes, which are presumably intercepted by Rh(II) catalysts to induce a 1,2-hydride migration. This sequence provides high levels of stereocontrol for the generation of simple acyclic (Z)-enol ethers. These enol ethers undergo either thermal or Lewis acid accelerated Claisen rearrangements to provide products of high diastereopurity. Also presented are cascade reactions, wherein a third chemical step occurs after the initial tandem sequence (i.e., Bamford−Stevens/Claisen/ene and Bamford−Stevens/Claisen/Cope).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja028020jDOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ja028020jPublisherSupporting Information
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2002 American Chemical Society. Received 5 August 2002. Published online 1 October 2002. Published in print 1 October 2002. The authors wish to thank the NSF (CHE-0135056), the Dreyfus Foundation, Merck Research Laboratories, and Abbott Laboratories for financial support.
Funders:
Funding AgencyGrant Number
NSFCHE-0135056
Camille and Henry Dreyfus FoundationUNSPECIFIED
Merck Research LaboratoriesUNSPECIFIED
Abbott LaboratoriesUNSPECIFIED
Issue or Number:42
DOI:10.1021/ja028020j
Record Number:CaltechAUTHORS:20170215-150235551
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170215-150235551
Official Citation:Non-Carbonyl-Stabilized Metallocarbenoids in Synthesis:  The Development of a Tandem Rhodium-Catalyzed Bamford−Stevens/Thermal Aliphatic Claisen Rearrangement Sequence Jeremy A. May and Brian M. Stoltz Journal of the American Chemical Society 2002 124 (42), 12426-12427 DOI: 10.1021/ja028020j
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74338
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Feb 2017 23:20
Last Modified:11 Nov 2021 05:26

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