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Asymmetric Induction in Intramolecular [2 + 2]-Photocycloadditions of 1,3-Disubstituted Allenes with Enones and Enoates

Carreira, Erick M. and Hastings, Curtis A. and Shepard, Mary S. and Yerkey, Lori A. and Millward, Dan B. (1994) Asymmetric Induction in Intramolecular [2 + 2]-Photocycloadditions of 1,3-Disubstituted Allenes with Enones and Enoates. Journal of the American Chemical Society, 116 (15). pp. 6622-6630. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180601-151522887

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Abstract

Irradiation of optically active allenes (89-92% ee) appended to enones and enoates affords alkylidenecyclobutane photoadducts with high levels of asymmetric induction (83-100%) derived exclusively from the allene fragment. The substrates studied include allenes tethered to enones such as 1,3-cyclohexanedionea nd 1,3-cyclopentanedione, as well as allenes tethered to functionalized coumarins. The enantiomer ratios of the photoadducts were quantified by derivatization of the products as the corresponding Mosher MTPA esters and analysis by ^1H NMR spectroscopy. The exo-methylenecyclobutanes obtained upon irradiation of allene-mumarins are isolated as single olefin diastereomers. Irradiation of a coumarin tethered at C(5) with an optically active allene affords an alkynyl-substituted oxepane with complete asymmetric induction.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ja00094a017DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ja00094a017PublisherSupporting Information
ORCID:
AuthorORCID
Carreira, Erick M.0000-0003-1472-490X
Additional Information:© 1994 American Chemical Society. Received January 3, 1994. C.A.H. thanks W. R. Grace and Co. for a summer fellowship award. M.S.S. is grateful to the Office of Naval Research for a graduate fellowship. We are grateful to Professor K. I. Hardcastle (California State University, Northridge) for obtaining an X-ray crystal structure of (±)-25. This research has been supported by a Beckman Young Investigator Award, the National Science Foundation (CHE-9221945), and a Camille and Henry Dreyfus New Faculty Award (NF-92-46).
Funders:
Funding AgencyGrant Number
W. R. Grace & Co.UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
NSFCHE-9221945
Camille and Henry Dreyfus FoundationNF-92-46
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arnold and Mabel Beckman Laboratories of Chemical Synthesis8959
Issue or Number:15
Record Number:CaltechAUTHORS:20180601-151522887
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180601-151522887
Official Citation:Asymmetric Induction in Intramolecular [2 + 2]-Photocycloadditions of 1,3-Disubstituted Allenes with Enones and Enoates Erick M. Carreira, Curtis A. Hastings, Mary S. Shepard, Lori A. Yerkey, and Dan B. Millward Journal of the American Chemical Society 1994 116 (15), 6622-6630 DOI: 10.1021/ja00094a017
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86758
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:01 Jun 2018 22:56
Last Modified:09 Mar 2020 13:18

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