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Difluoroacetaldehyde N ‐Triftosylhydrazone (DFHZ‐Tfs) as a Bench‐Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane
Author(s) -
Ning Yongquan,
Zhang Xinyu,
Gai Yi,
Dong Yuanqing,
Sivaguru Paramasivam,
Wang Yingying,
Reddy Bhoomireddy Rajendra Prasad,
Zai Giuseppe,
Bi Xihe
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202000119
Subject(s) - cyclopropanation , diazo , combinatorial chemistry , chemistry , density functional theory , functional group , molecule , catalysis , nanotechnology , computational chemistry , organic chemistry , materials science , polymer
Despite the growing importance of volatile functionalized diazoalkanes in organic synthesis, their safe generation and utilization remain a formidable challenge because of their difficult handling along with storage and security issues. In this study, we developed a bench‐stable difluoroacetaldehyde N ‐triftosylhydrazone (DFHZ‐Tfs) as an operationally safe diazo surrogate that can release in situ two low‐molecular‐weight diazoalkanes, diazoacetaldehyde (CHOCHN 2 ) or difluorodiazoethane (CF 2 HCHN 2 ), in a controlled fashion under specific conditions. DFHZ‐Tfs has been successfully employed in the Fe‐catalyzed cyclopropanation and Doyle–Kirmse reactions, thus highlighting the synthetic utility of DFHZ‐Tfs in the efficient construction of molecule frameworks containing CHO or CF 2 H groups. Moreover, the reaction mechanism for the generation of CHOCHN 2 from CF 2 HCHN 2 was elucidated by density functional theory (DFT) calculations.