Asymmetric Electrophilic Difluoromethylthiolation of Indanone-Based β-Keto Esters Using Difluoromethanesulfonyl Hypervalent Iodonium Ylides.

The first electrophilic diastereoselective direct introduction of the difluoromethylthio group is described. We used a chiral auxiliary-based approach to illustrate the versatility of our recently developed difluoromethanesulfonyl hypervalent iodonium ylide reagents for the difluoromethylthiolation of indanone-based β-keto esters. Chiral SCF₂H-featuring compounds were obtained in up to 93% ee value.

CFSOX (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CFSOCl.

The recent progresses of the application of trifluoromethanesulfonyl chloride, CFSOCl, in the formation of C-CF, C-SCF, C-SOCF, and C-Cl bonds are summarised in this second part of a two-part review published back-to-back on both sodium trifluoromethanesulfinate, CFSONa, (Part 1) and trifluoromethanesulfonyl chloride, CFSOCl (Part 2). There are many reactions in common between these two reagents but it should be noted that CFSOCl reacts under reductive conditions while CFSONa requires oxidative conditions. Electrophilic chlorination is obviously the exclusive preserve of CFSOCl that has been exploited with emphasis in enantioselective chlorination.

CFSOX (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation. Part 1: Use of CFSONa.

Sodium trifluoromethanesulfinate, CFSONa, and trifluoromethanesulfonyl chloride, CFSOCl, are two popular reagents that are widely used for the direct trifluoromethylation of a large range of substrates. Further, these two reagents are employed for the direct trifluoromethylsulfenylation and trifluoromethylsulfinylation, the introduction of the SCF and the S(O)CF group, respectively. In addition to the aforementioned reactions, the versatility of these two reagents is presented in other reactions such as sulfonylation and chlorination.

Nucleophilic Trifluoromethylthiolation of Cyclic Sulfamidates: Access to Chiral β- and γ-SCF Amines and α-Amino Esters.

The regio- and stereoselective ring opening of 1,2- and 1,3-sulfamidates with trifluoromethanethiolate anion is reported. This direct introduction of the whole SCF motif is a straightforward synthetic route toward β- and γ-SCF amines and α-amino acid derivatives. The utility of this reaction was further illustrated by incorporation of Cys(S-CF) into di- and tripeptides.

Novel Use of CF3SO2Cl for the Metal-Free Electrophilic Trifluoromethylthiolation.

The regioselective trifluoromethylthiolation of indole derivatives was achieved under reductive conditions with trifluoromethanesulfonyl chloride as the readily available source of electrophilic SCF3 and a phosphine as the reducing agent. It is a straightforward process free from any metal and also applicable for the trifluoromethylthiolation of other azaarenes, enamines, and enoxysilanes.

Synthesis of 1,2,3-Substituted Pyrroles from Propargylamines via a One-Pot Tandem Enyne Cross Metathesis-Cyclization Reaction.

Enyne cross metathesis of propargylamines with ethyl vinyl ether enables the one-pot synthesis of substituted pyrroles. A series of substituted pyrroles, bearing alkyl, aryl, and heteroaryl substituents, has been synthesized in good yields under microwave irradiation. The reactions are rapid and procedurally simple and also represent a facile entry to the synthetically challenging 1,2,3-substituted pyrroles.