131581-41-4Relevant academic research and scientific papers
Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine
Wang, Fei,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
, p. 344 - 351 (2014)
Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods. Results: The combination of (chlorodifluoromethyl)trimethylsilane (TMSCF2Cl) and triphenylphosphine (PPh3) can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyl)trimethylsilane (TMSCF2Br) and (trifluoromethyl)trimethylsilane (TMSCF3) in this reaction. Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.
Visible-light-promotedE-selective synthesis of α-fluoro-β-arylalkenyl sulfidesviathe deoxygenation/isomerization process
Li, Yuxiu,Li, Xiangqian,Li, Xiaowei,Shi, Dayong
supporting information, p. 2152 - 2155 (2021/03/06)
Regioselective synthesis of α-fluoro-β-arylalkenyl sulfides has been established withgem-difluoroalkenes and sodium sulfinates in a transition-metal-free manner. A series of control experiments were executed to demonstrate thiol radicals and anions as the proposed intermediates. Notably, regioselectiveZ→Eisomerization was achieved under green light irradiation in the absence of a photoinitiator.
Highly E-Selective Synthesis of α-Fluoro-β-arylalkenyl Sulfones from gem-Difluoroalkenes with Sodium Sulfinates
Li, Yuxiu,Li, Xiangqian,Li, Xiaowei,Shi, Dayong
, p. 6983 - 6993 (2021/05/06)
The straightforward synthesis of α-fluoro-β-arylalkenyl sulfones under transition-metal-and base-free conditions has been described, which displays broad functional group compatibility and high stereoselectivity. In particular, the strategy is also applied to the late-stage modification of complex natural products and drugs.
Pd-Catalyzed Selective Carbonylation of gem-Difluoroalkenes: A Practical Synthesis of Difluoromethylated Esters
Liu, Jiawang,Yang, Ji,Ferretti, Francesco,Jackstell, Ralf,Beller, Matthias
supporting information, p. 4690 - 4694 (2019/03/13)
The first catalyst for the alkoxycarbonylation of gem-difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac)2/1,2-bis((di-tert-butylphosphan-yl)methyl)benzene (btbpx) (L4) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.
Photoredox-Coupled F-Nucleophilic Addition: Allylation of gem-Difluoroalkenes
Liu, Haidong,Ge, Liang,Wang, Ding-Xing,Chen, Nan,Feng, Chao
supporting information, p. 3918 - 3922 (2019/02/19)
A novel strategy for the expedient construction of CF3-embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single-electron oxidation, electron-rich gem-difluoroalkenes, which otherwise are essentially reluctant towards F-nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α-CF3-substituted benzylic radical intermediates using cheap and readily available starting materials.
Stereoselective Synthesis of Z Fluoroalkenes through Copper-Catalyzed Hydrodefluorination of gem-Difluoroalkenes with Water
Hu, Jiefeng,Han, Xiaowei,Yuan, Yu,Shi, Zhuangzhi
supporting information, p. 13342 - 13346 (2017/10/17)
A copper catalytic system was established for the stereoselective hydrodefluorination of gem-difluoroalkenes through C?F activation to synthesize various Z fluoroalkenes. H2O is used as the hydrogen source for the fluorine acceptor moiety. This mild catalytic system shows good-functional group compatibility, accepting a range of carbonyls as precursors to the gem-difluoroalkenes, including aliphatic, aromatic, and α,β-unsaturated aldehydes and even ketones. It serves as a powerful synthetic method for the late-stage modification of complex compounds.
α,α-Difluoro-α-phenylsulfanylmethyl carbanion equivalent: a novel gem-difluoromethylenation of carbonyl compounds
Pohmakotr, Manat,Boonkitpattarakul, Kanhokthron,Ieawsuwan, Winai,Jarussophon, Suwatchai,Duangdee, Nongnaphat,Tuchinda, Patoomratana,Reutrakul, Vichai
, p. 5973 - 5985 (2007/10/03)
α,α-Difluoro-α-phenylsulfanyl-α-trimethylsilylmethane (PhSCF2SiMe3) has been demonstrated as an α,α-difluoro-α-phenylsulfanylmethyl carbanion equivalent. gem-Difluorophenylsulfanylmethylation of carbonyl compounds has been successful
DIFLUOROMETHYLDIPHENYLPHOSPHINE OXIDE. A NEW REAGENT FOR CONVERSION OF CARBONYL COMPOUNDS TO 1,1-DIFLUOROOLEFINS
Edwards, Michael L.,Stemerick, David M.,Jarvi, Esa T.
, p. 5571 - 5574 (2007/10/02)
Difluoromethyldiphenylphosphine oxide (5) was synthesized from chlorodifluoromethane and diphenylphosphine oxide.Reaction of 5 with a variety of ketones and aldehydes gave 1,1-difluoroolefins.Monofluoromethyldiphenylphosphine oxide (7) was also synthesize
