Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-Azepines, 1,4-Cyclohexadienes, 2H-Pyrans, and 1,3-Butadienes

07 June 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Herein, we report a versatile approach for the endocyclic ring-opening of bicyclic vinylcyclopropanes triggered by Heck arylations. Key step for this transformation is a [1,3]-migratory shift of Pd allowing the ring expansion of cyclopropanated pyrroles, piperidines, furans as well as cyclopentadienes to grant access to the corresponding 1,2-dihydropyridines, 2H-pyrans, 2,3-dihydro-1H-azepines and 1,4-cyclohexadienes, respectively. Additionally, gem-disubstituted cyclopropanated furans showed unexpected behavior by giving diastereoselectively asymmetrically substituted dienes. Mechanistic studies and theoretical calculations point towards a facile [1,3]-migratory shift of Pd along the cyclopropane moiety, which can successfully compete with the usual termination step of a Heck reaction via a syn-b-hydride elimination.

Keywords

palladium couplings
Heck reactions
dihydropyridines
azepines
cyclohexadienes
pyrans
butadienes

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.