(4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(Ⅱ)Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions  

(4S,4'S)-2,2'-(4,6-二苯并呋喃二基)双[4,5-二氢-4-苯基噁唑]-镍(Ⅱ)配合物催化高对映选择性氰亚胺的环加成反应

作　　者：Cao Xixian You Jun Liu Qiye Liu Bo Yu Yanchao Wu Wenju 曹茜娴;由君;刘其业;刘波;喻艳超;武文菊(哈尔滨理工大学材料科学与化学工程学院、绿色化工技术黑龙江省高校重点实验室,哈尔滨150080)

机构地区：[1]Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province,College of Materials Science and Chemical Engineering,Harbin University of Science and Technology,Harbin 150080

出　　处：《有机化学》2024年第7期2315-2332,共18页Chinese Journal of Organic Chemistry

基　　金：Project supported by the National Natural Science Foundation of China(Nos.22278098,21908034,22008045);the Natural Science Foundation of Heilongjiang Province(Nos.LH2021H001,LH2023B013)。

摘　　要：The Ni(Ⅱ)-chiral(4S,4'S)-2,2'-(4,6-dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole](DBFOX/Ph)-catalyzed asymmetric 1,3-dipolar cycloadditions of nitrile imines to N-α,β-unsaturated acylpyrazoles was presented.This tactic rendered a facile and feasible route to prepare the optically active tetrasubstituted 5-3,5-dimethylpyrazole acyl dihydropyrazole cy-cloadducts bearing one or two contiguous stereocenters in good yields(up to 97%yield)with high regioselectivities(100%)and enantioselectivities(up to 97.5%ee).Following that,chiral cycloadducts could be obtained consistently in good chemical yields with excellent enantioselectivities within the gram scale process,additionally,toward five kinds of derivatization reac-tions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.研究了Ni(Ⅱ)-手性(4S,4'S)-2,2'-(4,6-二苯并呋喃二基)双[4,5-二氢-4-苯基噁唑](DBFOX/Ph)金属配合物催化氰亚胺与N-(α,β-不饱和)酰基吡唑的不对称1,3-偶极环加成反应.该策略为制备包含四取代的一个或两个连续立体中心的手性5-3,5-二甲基吡唑酰基二氢吡唑环加成产物提供了一条简便可行的途径.研究结果表明,通过该反应可以高产率(97%)、高区域选择性(100%)和对映选择性(97.5%ee)地得到光学活性的环加成产物.在放大的克级反应中产物的收率和光学活性均可以很好地保持.此外,手性环加成产物可经过亲核和还原等5种反应生成含有不同取代基的手性二氢吡唑衍生物.

关 键 词：(4S 4'S)-2 2'-(4 6-dibenzofurandiyl)bis[4 5-dihydro-4-phenyloxazole](DBFOX/Ph) 1 3-dipolar cycloaddition nitrile imines N-α β-unsaturated acylpyrazole ENANTIOSELECTIVITY electronic circular dichroism(ECD)calculation 

分 类 号：O621.251[理学—有机化学]