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 

作者机构：School of Chemistry and Chemical EngineeringUniversity of JinanJinan 250022 Department of Chemistry and Nano ScienceEwha Womans UniversitySeoul 03760 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2022年第4卷第7期

页      面：2369-2381页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

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.) 

主　　题：bioinspired catalysis Rieske dioxygenase cis-dihydroxylation nonheme iron catalyst tetradentate nitrogen-donor ligand 

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 *** nonheme iron-catalyzed enantioselective cis-dihydroxylation meets the requirement of the modern synthetic chemistry from the atomic economy,green chemistry,and sustainable development ***,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 ***,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.