Details

Autor(en) / Beteiligte

• Fereyduni, Ehsan
• Sanders, Jacob N
• Gonzalez, Gabriel
• Houk, K N
• Grenning, Alexander J

Titel

Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes

Ist Teil von

• Chemical science (Cambridge), 2018-12, Vol.9 (46), p.8760-8764

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2018

Quelle

EZB Electronic Journals Library

Beschreibungen/Notizen

• A simple and modular route to arylcycloheptene scaffolds is reported. The two-step route from Knoevenagel adducts and allylic electrophiles is made possible through the design of a Cope rearrangement that utilizes a "traceless" activating group to promote an otherwise thermodynamically unfavorable transformation. Experimentally, the [3,3] rearrangement occurrs transiently at room temperature with a computed barrier of 19.5 kcal mol , which ultimately allows for three-component bis-allylation. Ring-closing metathesis delivers the arylcycloheptane and removes the activating group. This report describes the design and optimization of the methodology, scope and mechanistic studies, and computational analysis.