Nonheme Iron-Catalyzed Enantioselective cis-Dihydroxylation of Aliphatic Acrylates as Mimics of Rieske Dioxygenases  

作　　者：Jie Chen Xiu Luo Ying Sun Si Si Yuankai Xu Yong-Min Lee Wonwoo Nam Bin Wang 

机构地区：[1]School of Chemistry and Chemical Engineering,University of Jinan,Jinan 250022 [2]Department of Chemistry and Nano Science,Ewha Womans University,Seoul 03760

出　　处：《CCS Chemistry》2022年第7期2369-2381,共13页中国化学会会刊（英文）

基　　金：the National Natural Science Foundation of China(no.21771087 to B.W and no.21703080 to J.C);the NSF of Shandong Province(no.ZR2020YQ10 to B.W);Taishan Scholar Program of Shandong Province(no.tsqn201812078 to B.W.);the NRF of Korea(no.NRF-2021R1A3B1076539 to W.N.and no.NRF-2020R1I1A1A01074630 to Y.-M.L.).

摘　　要：Enantioselective cis-dihydroxylation of alkenes represents an ideal route to synthesize enantioenriched syn-2,3-dihydroxy esters that are important structural motifs in numerous biologically and pharmaceutically relevant molecules.Bioinspired nonheme iron-catalyzed enantioselective cis-dihydroxylation meets the requirement of the modern synthetic chemistry from the atomic economy,green chemistry,and sustainable development perspectives.However,nonheme iron-catalyzed enantioselective cis-dihydroxylation is much underdeveloped because of the formidable challenges of controlling chemo-and enantioselectivities and product selectivity caused by the competitive epoxidation,cis-dihydroxylation,and overoxidation reactions.Herein,we disclose the fabrication of a biologically inspired nonheme iron complex-catalyzed enantioselective cis-dihydroxylation of multisubstituted acrylates using hydrogen peroxide(H_(2)O_(2))as the terminal oxidant by controlling the non-ligating or weakly ligating counterions of iron(Ⅱ)complexes,demonstrating a dramatic counteranion effect on the enantioselective cisdihydroxylation of olefins by H_(2)O_(2) catalyzed by nonheme iron complexes.A range of structurally disparate alkenes were transformed to the corresponding syn-2,3-dihydroxy esters in practically useful yields with exquisite chemo-and enantioselectivities(up to 99% ee).Given the mild and benign nature of this biologically inspired oxidation system as well as the ubiquity and synthetic utility of enantioenriched syn-2,3-dihydroxy esters as pharmaceuticals candidates and natural products,we expect that this strategy could serve as a promising complement to the well-known Sharpless asymmetric dihydroxylation,which is the chemical reaction of an alkene with OsO_(4) to produce a vicinal diol.

关 键 词：bioinspired catalysis Rieske dioxygenase cis-dihydroxylation nonheme iron catalyst tetradentate nitrogen-donor ligand 

分 类 号：O62[理学—有机化学]