Fluoroalkyl N-Triftosylhydrazones as Easily Decomposable Diazo Surrogates for Asymmetric [2+1] Cycloaddition: Synthesis of Chiral Fluoroalkyl Cyclopropenes and Cyclopropanes

被引:32
|
作者
Zhang, Xinyu [1 ]
Tian, Chunqi [1 ]
Wang, Zhanjing [1 ]
Sivaguru, Paramasivam [1 ]
Nolan, Steven P. [2 ,3 ]
Bi, Xihe [1 ,4 ]
机构
[1] Northeast Normal Univ, Dept Chem, Changchun 130024, Peoples R China
[2] Univ Ghent, Dept Chem, B-9000 Ghent, Belgium
[3] Univ Ghent, Ctr Sustainable Chem, B-9000 Ghent, Belgium
[4] Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China
关键词
fluoroalkyl N-triftosylhydrazones; asymmetric [2+1] cycloaddition; cyclopropene; cyclopropane; low temperature; IN-SITU GENERATION; C-C BOND; ENANTIOSELECTIVE SYNTHESIS; CATALYZED INSERTION; RECENT PROGRESS; BORONIC ACIDS; TRIFLUOROMETHYL; TOSYLHYDRAZONES; REAGENTS; CONSTRUCTION;
D O I
10.1021/acscatal.1c01483
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The development of asymmetric carbene transfer reactions using N-sulfonylhydrazones as the diazo surrogate is a long-term issue in organic synthesis since N-sulfonylhydrazones commonly require high temperatures for their decomposition to release reactive diazo compounds. We report on the use of fluoroalkyl-aryl ketone N-triftosylhydrazones as a class of N-sulfonylhydrazone capable of decomposing below 0 degrees C (to -40 degrees C). Their application in asymmetric [2 + 1] cycloadditions with alkynes and alkenes catalyzed by a chiral rhodium catalyst is described. This protocol affords a wide variety of fluoroalkylated cyclopropenes and cyclopropanes in high yields and high enantioselectivity and demonstrates broad functional group tolerance. It is noteworthy that these small-ring products feature a fluoroalkyl chiral quaternary carbon center. The origin of enantioselectivity for the cyclopropenation reaction of N-triftosylhydrazones with alkynes was rationalized by density functional theory calculations.
引用
收藏
页码:8527 / 8537
页数:11
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