Mukaiyama Michael addition of silyl enol ethers 13 to the 1,2-quinone-4-carboxylate 6 (formed in situ by oxidation of the catechol ester 8) afforded the 2-subsituted 7-hydroxybenzofuran-4-carboxylates 14 in fair to good yields. Alkyl and aryl systems work well, but highly electron-rich silyl enol ethers could not be used because of competing oxidation.

LUMO-lowering organocatalysis has been extended to promote the conjugate addition of S-alkyl and -pyrrolyl silylketene acetals to α,β-unsaturated aldehydes, yielding both, syn and anti Mukaiyama-Michael products with high levels of enantioselectivity. This strategy allows for the generation of chemically useful 1,5-dicarbonyl systems and again highlights the utility of organocatalysis.

A class of monomeric nuphar analogues that are either epimeric at C1 and C1' or lack the naturally occurring methyl group at those positions were synthesized and evaluated for biological activity. The syntheses feature enantioselective vinylogous Mukaiyama-Mannich (vM-Mannich) reactions catalyzed by chiral phosphoric acids that proceed with excellent diastereoselectivity. Biological assays reve...

The synthesis of a second-generation cobalt catalyst for the formation of trans-THF products via the Mukaiyama aerobic oxidative cyclization is reported. Two procedures have been developed with the new water-soluble catalyst that give superior yields and greatly simplify purification compared to the previous catalysts.

Asymmetric catalysis of the Mukaiyama aldol reaction has been reported with complexes derived from Al, B, Sn(II), and Ti(IV).l The levels of asymmetric induction for the addition of propionate-, isobutyrate-, and acetate-derived silyl thioketene acetals to aldehydes parallel those obtained with chiral-auxiliarybased methodologies.2 However, silyl ketene acetals derived from 0-alkyl acetates uni...

The Cover picture is a photo of the late Professor Teruaki Mukaiyama and his wife, Hiroko, taken whilst he was graduate student at Tokyo Institute Technology. founding editor Chemical Record Essay on life by Masahiro Murakami (DOI: 10.1002/tcr.202000105) coincides with 20th anniversary Journal.

Mukaiyama s classic catalytic asymmetric aldol reaction with enolsilanes has been improved upon over the years; now new approaches to the reaction have been developed. Those reviewed here are the use of new transition metal based catalysts for the aldol reaction using silyl enolates, the use of other O-silylated nucleophiles, tin-modified or even unmodified ketones as substrates, and the use of...