Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (7): 2315-2332.DOI: 10.6023/cjoc202311029 Previous Articles     Next Articles

ARTICLES

(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

曹茜娴, 由君*(), 刘其业, 刘波, 喻艳超, 武文菊*()   

  1. 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
  • 收稿日期:2023-11-27 修回日期:2024-02-27 发布日期:2024-03-28
  • 基金资助:
    国家自然科学基金(22278098); 国家自然科学基金(21908034); 国家自然科学基金(22008045); 黑龙江省自然科学基金(LH2021H001); 黑龙江省自然科学基金(LH2023B013)

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

Xixian Cao, Jun You(), Qiye Liu, Bo Liu, Yanchao Yu, Wenju Wu()   

  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
  • Received:2023-11-27 Revised:2024-02-27 Published:2024-03-28
  • Contact: E-mail: youjunjun@126.com;wuwenju1017@163.com
  • Supported by:
    National Natural Science Foundation of China ((22278098); National Natural Science Foundation of China ((21908034); National Natural Science Foundation of China ((22008045); Natural Science Foundation of Heilongjiang Province(LH2021H001); Natural Science Foundation of Heilongjiang Province(LH2023B013)

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 cycloadducts 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 reactions like nucleophilic and reduction for further conversion of chiral cycloadducts to related chiral dihydropyrazole derivatives encompassing different substituents.

Key words: (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