Département de Chimie, Université de Montréal , P.O. Box 6128, Station Centre-ville, Montréal, Québec H3C 3J7, Canada.
Org Lett. 2017 Oct 6;19(19):5066-5069. doi: 10.1021/acs.orglett.7b02275. Epub 2017 Sep 26.
Azacyclo- and azabicycloalkanone peptidomimetics were synthesized regio- and diastereoselectively by iodoacetoxylation and transannular amidation reactions on unsaturated lactam precursors contingent on ring size, olefin position, solvent, and hypervalent iodine(III) reagent. 4-Iodopyrrolizidinone 1, 7-iodoindolizidinone 2, and 4-iodo-5-acetoxylactams (e.g., 6 and 7) were made stereospecifically from 7-9-membered olefins 16, iodine, and hypervalent iodine(III) in acetonitrile or toluene, respectively. X-ray crystallography demonstrated potential for mimicry of natural peptide turn side chain and backbone conformations.
氮杂环烷酮和氮杂环丁烷肽拟似物通过不饱和内酰胺前体的碘乙氧羰酰化和环间酰胺化反应，以区域和立体选择性方式合成，这取决于环大小、烯烃位置、溶剂和高价碘(III)试剂。4-碘基吡咯烷酮 1、7-碘吲哚嗪酮 2 和 4-碘-5-乙氧羰基内酰胺（例如 6 和 7）分别从 7-9 元烯烃 16、碘和高价碘(III)在乙腈或甲苯中立体特异性地合成。X 射线晶体学证明了模拟天然肽转角侧链和骨架构象的潜力。
