Facile Synthesis of Chiral α‐Difluoromethyl Amines from N‐(tert‐Butylsulfinyl)aldimines

Highly Stereoselective Trichloromethylation of N‐(tert‐Butylsulfinyl)aldimines: Facile Synthesis of Chiral α‐Trichloromethylamines

“…[19] The absolute configuration of sulfinamide 3a was determined by single-crystal X-ray analysis (Figure 1a), and was consistent with our prediction based on a commonly used nonchelation-controlled transition-state mode to give the Cram products (Figure 1b), in which the tert-butyl group adopts the antiperiplanar arrangement with respect to the C=N bond. [15,20] However, recent studies indicated that, mainly due to the contribution of intramolecular hydrogen bonding of the oxygen with the imine hydrogen, the sulfinyl oxygen in a s-cis arrangement with respect to the C=N bond is the most stable conformation for the N-(phenylsulfinyl)imine. [21] The approach of the nucleophile (CCl 3 -) to this conformation would also lead to the observed stereoselectivity as shown in Figure 1c.…”

“…As part of our continuing efforts in the development of efficient methodologies for the synthesis of chiral α-(halogenated methyl)amines, [15] herein we report the first stereoselective synthesis of α-trichloromethylamines by using readily accessible trimethyl(trichloromethyl)silane (TMSCCl 3 , 1).…”

Theoretical study of nucleophilic halogenalkylation of propylene oxide with halogenmethane and dihalogenmethane anion

“…1,2 Nucleophilic fluoroalkylation, typically involving the transfer of a fluorine-bearing carbanion to an electrophile, has been widely studied and applied to synthesize fluorine-containing materials and bioactive molecules. [3][4][5][6][7][8][9][10][11][12][13][14][15] Despite the availability of a variety of good methods and numerous examples of nucleophilic fluoroalkylation of various substrates, [4][5][6][7][8] there are only a few examples in the literature related to nucleophilic fluoroalkylation of simple epoxides. The possible reason, as stated in the literature, 3 can be attributed to the intrinsic property of the fluorine-bearing carbanion, as well as its weak nucleophilicity toward epoxides.…”

Fluoride ion-mediated nucleophilic fluoroalkylation of alkyl halides with Me3SiCF2SPh: Synthesis of PhSCF2- and CF2H-containing compounds

“…As a result, organofluorine chemistry has attracted enormous attention in the field of pharmaceutical and agricultural chemistry, as exemplified by the fact that fluorine substituents have become widespread and important drug components [8,9]. Among fluorine-containing moities, the difluoromethyl group (CF 2 H) is of significant interest [10][11][12][13], since the latter one is believed to act as an isopolar and isosteric analog of the CH 2 OH group [14,15]. Moreover, CF 2 H is able to act as a lipophilic hydrogen bond donor through hydrogen bonding [11].…”