331941-37-8Relevant articles and documents
Difluoroacetaldehyde N-Triftosylhydrazone (DFHZ-Tfs) as a Bench-Stable Crystalline Diazo Surrogate for Diazoacetaldehyde and Difluorodiazoethane
Bi, Xihe,Dong, Yuanqing,Gai, Yi,Ning, Yongquan,Reddy, Bhoomireddy Rajendra Prasad,Sivaguru, Paramasivam,Wang, Yingying,Zanoni, Giuseppe,Zhang, Xinyu
supporting information, p. 6473 - 6481 (2020/03/10)
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.
Highly Diastereo- and Enantioselective Synthesis of Nitrile-Substituted Cyclopropanes by Myoglobin-Mediated Carbene Transfer Catalysis
Chandgude, Ajay L.,Fasan, Rudi
supporting information, p. 15852 - 15856 (2018/11/23)
A chemobiocatalytic strategy for the highly stereoselective synthesis of nitrile-substituted cyclopropanes is reported. The present approach relies on an asymmetric olefin cyclopropanation reaction catalyzed by an engineered myoglobin in the presence of ex situ generated diazoacetonitrile within a compartmentalized reaction system. This method enabled the efficient transformation of a broad range of olefin substrates at a preparative scale with up to 99.9 % de and ee and up to 5600 turnovers. The enzymatic product could be further elaborated to afford a variety of functionalized chiral cyclopropanes. This work expands the range of synthetically valuable, abiotic transformations accessible through biocatalysis and paves the way to the practical and safe exploitation of diazoacetonitrile in biocatalytic carbene transfer reactions.
Towards nitrile-substituted cyclopropanes-a slow-release protocol for safe and scalable applications of diazo acetonitrile
Hock, Katharina J.,Spitzner, Robin,Koenigs, Rene M.
supporting information, p. 2118 - 2122 (2017/07/24)
Diazo acetonitrile has long been neglected despite its high value in organic synthesis due to a high risk of explosions. Herein, we report our efforts towards the transient and safe generation of this diazo compound, its applications in iron catalyzed cyclopropanation and cyclopropenation reactions and the gram-scale synthesis of cyclopropyl nitriles.
Macroporous chiral ruthenium porphyrin polymers: A new solid-phase material used as a device for catalytic asymmetric carbene transfer
Ferrand, Yann,Le Maux, Paul,Simonneaux, Gerard
, p. 3829 - 3836 (2007/10/03)
A chiral ruthenium porphyrin complex, functionalized with four vinyl groups, has been polymerized with styrene, divinylbenzene (or ethylene glycol dimethacrylate) to obtain supported ruthenium complexes. The asymmetric addition of ethyl diazoacetate (or d
A novel approach to enantiopure cyclopropane compounds from biotransformation of nitriles
Wang, Mei-Xiang,Feng, Guo-Qiang
, p. 1575 - 1583 (2007/10/03)
Rhodococcus sp. AJ270, a powerful and versatile nitrile hydratase/amidase containing microbial whole-cell system, catalyzed the enantioselective hydrolysis of both racemic trans- and cis-2-arylcyclopropanecarbonitriles to afford the corresponding amides and acids with enantiomeric excesses as high as >99%. The reaction rate and enantioselectivity observed for both nitrile hydratase and amidase were also strongly dependent upon the nature of the substituent and substitution pattern on the benzene ring of the substrates. The application of and the advantages of biotransformation of nitriles were demonstrated by preparing (1S,2R)-2-phenylcyclopropylamine and (1R,2R)-2-phenylcyclopropylmethylamine through facile and straightforward chemical manipulations of (1S,2S)-2-phenylcyclopropanecarboxylic acid and (1R,2R)-2-phenylcyclopropanecarboxamide, respectively.
