Homoallyl alcohol as an allylation reagent for termination of the Catellani–Lautens reaction via retro-allylation

Abstract

A palladium/norbornene-catalyzed ortho-amination/allylation of aryl iodides was developed for the construction of ortho-aminated allylbenzene by using N-benzoyloxyamines as the amination reagent and homoallyl alcohols as the allylation reagent. The reaction...

Palladium-catalyzed allylic allenylation of homoallyl alcohols with propargylic carbonates

“…Based on the previous reports on palladium-catalyzed propargylic carbonates cross-coupling reactions 9–15 and palladium-catalyzed retro-allylation with homoallyl alcohols, 3–5 a plausible mechanism is proposed for this transformation (Scheme 3). The initial S N 2′-type oxidative addition of propargylic carbonates 1 to Pd(0) leads to the allenylic palladium intermediate A , followed by reaction with homoallyl alcohol 2a to finish intermediate B .…”

“…In the course of our ongoing research on the palladiumcatalyzed cross-coupling reactions, 4,5,16 we envisioned that homoallyl alcohols could be used as allyl reagents in palladium-catalyzed reaction of propargylic alcohol derivatives. Herein we disclose a palladium-catalyzed allylic allenylation of homoallyl alcohols with propargylic carbonates to access to allyl allenes (Scheme 1c).…”

“…4 We further developed a palladium/norbornene-catalyzed ortho -amination/allylation of aryl iodides for the construction of ortho -aminated allylbenzene by using homoallyl alcohols as the allylation reagent. 5 Although considerable advances of the palladium-catalyzed retro-allylation with homoallyl alcohols, this well-established protocol is restricted to allylic arylation and allylic alkylation.…”