Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Dr. Yongquan Ning, Xinyu Zhang, Yi Gai, Yuanqing Dong, Dr. Paramasivam Sivaguru, Yingying Wang, Dr. Bhoomireddy Rajendra Prasad Reddy, Prof. Giuseppe Zanoni, Prof. Xihe Bi
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引用次数: 30

Abstract

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 (CHOCHN2) or difluorodiazoethane (CF2HCHN2), 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 CF2H groups. Moreover, the reaction mechanism for the generation of CHOCHN2 from CF2HCHN2 was elucidated by density functional theory (DFT) calculations.

Abstract Image

二氟乙醛n -三甲基腙(DFHZ-Tfs)作为二氮乙醛和二氟重氮乙烷的稳定结晶重氮替代物
尽管挥发性官能化重氮烷烃在有机合成中的重要性日益增加,但由于其难以处理以及储存和安全问题,其安全生产和利用仍然是一个巨大的挑战。在这项研究中,我们开发了一种稳定的二氟乙醛n -三甲基腙(DFHZ-Tfs)作为一种操作安全的重氮替代品,可以在特定条件下以可控的方式原位释放两种低分子量重氮烷烃,重氮乙醛(CHOCHN2)或二氟重氮乙烷(CF2HCHN2)。dfhs - tfs已成功应用于fe催化的环丙烷化反应和Doyle-Kirmse反应中,从而突出了dfhs - tfs在高效构建含有CHO或CF2H基团的分子框架方面的合成用途。利用密度泛函理论(DFT)分析了CF2HCHN2生成CHOCHN2的反应机理。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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