2021 年 79 巻 5 号 p. 391-405
Separation and extraction of nucleophilicity from Brønsted basicity are a fundamental interest in organometallic chemistry. This topic is especially important for realizing protecting group-minimum synthesis of multifunctional molecules, e.g. sugars and drug leads. Summarizing our recent achievements, here I showcase that copper(I)-conjugated carbon nucleophiles, such as allylcopper, allenylcopper, copper alkynides, and copper enolates, are uniquely functional under protic environments without being decomposed. The soft characteristics of copper(I)-conjugated carbon nucleophiles are crucial for this chemoselectivity. The concept of hard anion-conjugated soft metal complex catalysis (HASM) is the basis for the catalytic generation of the active nucleophiles from stable molecules. Introducing chiral ligands to the copper catalysts allows for the catalyst-controlled stereoselectivity. Combining those strengths of the copper(I) catalysis, we achieved anomeric C-C bond formation of unprotected sugars, short and stereodivergent synthesis of sialic acids, use of hydrocarbon eneynes in asymmetric synthesis, and asymmetric domino/iterative aldehyde aldol reactions for the synthesis of 1,3-polyols, which are the topics of this review.