Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 42, Pages 13518-13523Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b06656
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Funding
- National Science Foundation [CHE-1361104]
- UCLA
- CBI
- NSF [OCI-1053575]
- Direct For Mathematical & Physical Scien [1361104] Funding Source: National Science Foundation
- Division Of Chemistry [1361104] Funding Source: National Science Foundation
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The transannular [6 + 4] cydoaddition proposed as a step in the biosynthesis of heronamide A has been modeled using density functional theory. The proposed cydoaddition 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(-1) 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] cydoaddition in the biogenesis of heronamide A and may provide insights to designing substrates that selectively undergo [6 + 4] cydoaddition to form unbridged 10-membered rings.
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