Cascade aryne insertion/vinylogous aldol reaction of vinyl-substituted β-keto/enol carbonyls

Abstract

Cyclic and acyclic vinyl substituted β-keto/enol carbonyl substrates, on reaction with arynes, result in differentially substituted naphthyl carbocycles, hitherto difficult to synthesize with existing protocols. While the substitutions on the...

Regiocontrol by Halogen Substituent on Arynes: Generation of 3-Haloarynes and Their Synthetic Reactions

“…The precursors 68a-d were used in various aryne-based reactions. [32][33][34][35][36][37][38] As an example for regioselective insertion of 3-haloarynes into a  bond, the fluorostannylation of arynes was reported (Scheme 20). 32 Precursors 68b and 68c in the presence of KF and 18-crown-6 in DME at 0 °C generate 3-haloarynes that react with tributyltin fluoride to give 103b and 103c, the products of Ar-F and Ar-Sn bond-formation at adjacent positions in the aromatic ring.…”

“…Novel methodology for the synthesis of naphthalene derivatives was reported. 38 The reaction of precursor 68b with 2-oxocyclonon-8-enecarboxylate 114 in the presence of KF and 18-crown-6 gave the naphthyl carbocycle 115 in 64% yield. This cascade transformation involves the insertion of 3-chloroaryne into the C-C bond of 114 followed by a vinylogous aldol reaction.…”

Access to Spiroindanolactones/lactams through an Aryne Insertion/Spirocyclization Strategy

“…Hopf and co-workers reported the synthesis of 4-aryl-3-(2 H )-furanones by an α-arylation/cyclization strategy of 4-haloacetoacetate with arynes (Scheme b) . Our group is actively engaged in expanding the scope of aryne chemistry toward medicinally relevant bioactive molecules . We envisaged that reaction of aryne with α-haloacetyl lactones under mild reaction conditions might be a new strategy for the synthesis of spiroindanolactones.…”