Synthesis ofgem-Difluorocyclopropa(e)nes and O-, S-, N-, and P-Difluoromethylated Compounds with TMSCF2Br
摘要:
Two-in-one: Me3 SiCF2 Br is an efficient difluorocarbene source and is compatible with both neutral and aqueous basic conditions. Bromide-ion-initiated [2+1] cycloaddition with alkenes/alkynes and hydroxide ion promoted α-addition with (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, and H-phosphine oxides give the corresponding gem-difluorinated compounds with broad functional-group tolerance.
An aromatic polyether comprising structural units derived from a halosulfone sulfonate having structure (I):
wherein R
1
is a C
3
-C
25
aromatic radical, a C
3
-C
25
cycloaliphatic radical, or a C
1
-C
10
aliphatic radical; M is hydrogen or a charge balancing cation; Y
1
is independently at each occurrence a halogen; “t” is an integer having a value of 1 or 2; “s” is an integer having a value 0 to 3, “b” is an integer having a value 1 to 4; and “c” is an integer having a value 1 to 20. Also provided are methods of preparing the aromatic polyethers, and compositions including the aromatic polyethers.
Radical Difluororomethylation of Thiols with Difluoromethylphosphonium Triflate under Photoredox Catalysis
作者:Yang Ran、Qing-Yu Lin、Xiu-Hua Xu、Feng-Ling Qing
DOI:10.1021/acs.joc.7b01041
日期:2017.7.21
A convenient, visible light-induced radical difluoromethylation of aryl-, heteroaryl-, and alkylthiols with difluoromethyltriphenylphosphonium triflate was developed to afford various difluoromethyl thioethers in moderate to excellent yields. The key reaction features include the use of a readily available CF2H radical source, mild reaction conditions, and excellent chemoselective "thiol-difluoromethylation.
<i>N</i>-Tosyl-<i>S</i>-difluoromethyl-<i>S</i>-phenylsulfoximine: A New Difluoromethylation Reagent for S-, N-, and C-Nucleophiles
作者:Wei Zhang、Fei Wang、Jinbo Hu
DOI:10.1021/ol900567c
日期:2009.5.21
The first alpha-difluoromethyl sulfoximine compound, 2, was successfully prepared by using the copper(II)-catalyzed nitrene transfer reaction. Compound 2 was found to be a novel and efficient difluoromethylation reagent for transferring the CF2H group to S-, N-, and C-nucleophiles. Deuterium-labeling experiments suggest that a difluorocarbene mechanism is involved in the current difluoromethylation reactions.
Synthesis of<i>gem</i>-Difluorocyclopropa(e)nes and O<i>-</i>, S<i>-</i>, N<i>-</i>, and P-Difluoromethylated Compounds with TMSCF<sub>2</sub>Br
作者:Lingchun Li、Fei Wang、Chuanfa Ni、Jinbo Hu
DOI:10.1002/anie.201306703
日期:2013.11.18
Two-in-one: Me3 SiCF2 Br is an efficient difluorocarbene source and is compatible with both neutral and aqueous basic conditions. Bromide-ion-initiated [2+1] cycloaddition with alkenes/alkynes and hydroxide ion promoted α-addition with (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, and H-phosphine oxides give the corresponding gem-difluorinated compounds with broad functional-group tolerance.