A Versatile Route to Acyl (MIDA)Boronates

Abstract

A modular approach to highly functional acyl (MIDA)boronates is described. It involves the generation of the hitherto unknown radical derived from acetyl (MIDA)boronate and its capture by various alkenes, including electronically unbiased, unactivated alkenes. In contrast to the anion of acetyl (MIDA)boronate, which has not so far been employed in synthesis, the corresponding radical is well behaved and readily produced from the novel α‐xanthyl acetyl (MIDA)boronate. This shelf‐stable, easily prepared solid is a convenient acyl (MIDA)boronate transfer agent that provides a direct entry to numerous otherwise inaccessible structures, including latent 1,4‐dicarbonyl derivatives that can be transformed into B(MIDA) substituted pyrroles and furans. A competition experiment indicated the acyl (MIDA)boronate substituted radical to be more stable than the all‐carbon acetonyl radical but somewhat less reactive in additions to alkenes.

Some Aspects of α-(Acyloxy)alkyl Radicals in Organic Synthesis

“…Synthesis of aliphatic and alicyclic α-(acyloxy)alkyl xanthates by radical addition to vinyl esters. Xa = -SC(=S)OEt; Piv = pivalate; Bz = benzoate; PhthN = phthalimido[13,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. Scheme 4.…”