Transannular [6 + 4] and Ambimodal Cycloaddition in the Biosynthesis of Heronamide A.
The transannular [6 + 4] cycloaddition proposed as a step in the biosynthesis of heronamide A has been modeled using density functional theory. The proposed cycloaddition is highly stereoselective, affording a single product. The reaction proceeds through an ambimodal transition state that directly...
| Published in: | Journal of the American Chemical Society Vol. 137; no. 42; pp. 13518 - 13524 |
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| Main Authors: | , , |
| Format: | Article |
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American Chemical Society
10/28/2015
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| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=110948474&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 110948474 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/28/2015 vid: 137 iid: 42 pid: 997 pub: American Chemical Society artinfo: ui: 110948474 10.1021/jacs.5b06656 ppf: 13518 ppct: 6 formats: tig: atl: Transannular [6 + 4] and Ambimodal Cycloaddition in the Biosynthesis of Heronamide A. aug: au: Peiyuan Yu Patel, Ashay Houk, K. N. affil: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, California 90095, United States su: Ring formation (Chemistry) Biosynthesis Amides Density functional theory Biochemical substrates Thermodynamics sug: subj: Ring formation (Chemistry) Biosynthesis Amides Density functional theory Biochemical substrates Thermodynamics ab: The transannular [6 + 4] cycloaddition proposed as a step in the biosynthesis of heronamide A has been modeled using density functional theory. The proposed cycloaddition is highly stereoselective, affording a single product. The reaction proceeds through an ambimodal transition state that directly leads to a [4 + 2] adduct in addition to the observed [6 + 4] adduct. Interconversion of these adducts is possible via a facile Cope rearrangement. The [6 + 4] adduct is thermodynamically more stable than the [4 + 2] adduct by 5.2 kcal mol due to a combination of the ring and steric strain in the [4 + 2] product. The results strongly support the plausibility of the proposed transannular [6 + 4] cycloaddition in the biogenesis of heronamide A and may provide insights to designing substrates that selectively undergo [6 + 4] cycloaddition to form unbridged 10-membered rings. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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