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:

URL	URL Type	Description
http://dx.doi.org/10.1021/ja028020j	DOI	Article
http://pubs.acs.org/doi/suppl/10.1021/ja028020j	Publisher	Supporting Information

ORCID:

Author	ORCID
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 Agency	Grant Number
NSF	CHE-0135056
Camille and Henry Dreyfus Foundation	UNSPECIFIED
Merck Research Laboratories	UNSPECIFIED
Abbott Laboratories	UNSPECIFIED

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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

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ID Code:

74338

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CaltechAUTHORS

Deposited By:

Ruth Sustaita

Deposited On:

15 Feb 2017 23:20

Last Modified:

11 Nov 2021 05:26

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