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Published July 27, 1994 | Version Supplemental Material
Journal Article Open

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

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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.

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).

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Supplemental Material - ja00094a017_si_001.pdf

Supplemental Material - ja6622.pdf

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Additional details

Identifiers

Eprint ID
86758
DOI
10.1021/ja00094a017
Resolver ID
CaltechAUTHORS:20180601-151522887

Related works

Describes
10.1021/ja00094a017 (DOI)

Funding

W. R. Grace & Co.
Office of Naval Research (ONR)
Arnold and Mabel Beckman Foundation
NSF
CHE-9221945
Camille and Henry Dreyfus Foundation
NF-92-46

Dates

Created
2018-06-01
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Updated
2021-11-15
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Caltech Custom Metadata

Other Numbering System Name
Arnold and Mabel Beckman Laboratories of Chemical Synthesis
Other Numbering System Identifier
8959