Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China. Fax: (+86) 512-6588-0334.
Chem Rec. 2018 Sep;18(9):1292-1305. doi: 10.1002/tcr.201700069. Epub 2018 Mar 7.
In this account, we describe our recent progress on transition-metal-free-catalyzed cross-coupling reactions using tetrabutylammonium iodide (TBAI) as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant. A rich variety of important organic compounds including α-acyloxy ethers, tert-butyl peresters, allylic esters, amides, α-amino nitriles, fully substituted pyrazoles, N-sulfonyl formamidines, α-amino acid esters, cyanomethyl esters, N-nitrosamines, and 3-acyloxy-2,3-dihydrobenzofurans have been successfully achieved in high chemoselectivity. Mechanistic studies suggested that TBAI could decompose TBHP to BuO and BuOO or be oxdized to (hypo)iodite by TBHP.
在本报告中，我们描述了最近在过渡金属催化的交叉偶联反应方面的进展，使用四丁基碘化铵（TBAI）作为催化剂，叔丁基过氧化氢（TBHP）作为氧化剂。成功地实现了多种重要的有机化合物的合成，包括α-酰氧基醚、叔丁基过氧酯、烯丙基酯、酰胺、α-氨基腈、全取代吡唑、N-磺酰基甲脒、α-氨基酸酯、氰甲基酯、N-亚硝胺和 3-酰氧基-2,3-二氢苯并呋喃，具有高化学选择性。机理研究表明，TBAI 可以将 TBHP 分解为 BuO 和 BuOO，或者被 TBHP 氧化为（次）碘酸盐。
