Synthesis of Diverse γ-Aryl-β-ketoesters via Aryne Intermediates Generated by C–C Bond Cleavage

Abstract

A synthetic method for diverse γ-aryl-β-ketoesters through γ-aryl-β-ketoester-type arynes triggered by C–C bond cleavage has been developed. The Mukaiyama aldol reaction of 6-(triflyloxy)­benzocyclo­butenones with ketene silyl acetals and subsequent treatment of resulting 6-(triflyloxy)­benzo­cyclo­butenols with a base triggered the efficient generation of γ-aryl-β-ketoester-type arynes, which reacted with various arynophiles to provide a wide range of γ-aryl-β-ketoesters. The synthetic utility of the method was demonstrated by the synthesis of an analog of ALK inhibitor.

Biobased C6-Furans in Organic Synthesis and Industry: Cycloaddition Chemistry as a Key Approach to Aromatic Building Blocks

“…A broad scope of benzoannulated 7-oxanorbornenes can be obtained via this approach. The utilization of diarynes (Table ) and polycyclic arynes (Table ) leads to the formation of condensed polycyclic systems. …”

Organocatalytic hydration of activated alkynes

“…We next turned our attention towards β-ketoesters which are fundamental synthons in organic chemistry. (37)(38)(39) Preliminary experiments starting from commercially available methyl ester 4a(X) using stoichiometric catalyst showed that L-Cys can also facilitate this transformation.…”

Cyclobutane based “overbred intermediates” and their exploration in organic synthesis

“…The arynes were next trapped with several arynophiles to achieve complex ring systems ( 104 ) as depicted in Scheme 20b. 37…”