ポリケタイドの全合成研究における新展開—不斉補助基からの脱却—

抄録

The complex issues of stereoselectivity posed by polyketides are most often addressed through the use of chiral auxiliaries, chiral reagents, and premetalated nucleophiles. Prof. Krische’s approach takes advantage of carbonyl allylation and crotylation protocols, wherein primary alcohol dehydrogenation concurrently triggers aldehyde formation and reductive generation of allyliridium nucleophiles, enabling asymmetric carbonyl allylation and crotylation directly from the alcohol oxidation level. His approach circumvents additional manipulations associated with the use of non-native functional groups or substructures to mediate bond construction, as evident in the use of chiral auxiliaries, and minimizes (re)functionalizations, especially redox manipulations.