A Cu-catalyzed aerobic oxidative reaction between sulfonyl hydrazides and alcohols has been developed. In this reaction, sulfonyl hydrazides act as the sulfinic acid precursors to react with alcohols, resulting in sulfinic esters with up to 72 % yield. This catalytic system tolerates a wide range of sulfonyl hydrazide substrates, and represents a new strategy for the transformation of readily available sulfonyl hydrazides.

Currently, there is a great demand for the development of new methods for the preparation of fluorine containing compounds. However, biologically relevant molecules bearing fluoroalkyl groups other than CF₃ still remain virtually unexplored. Herein, we report a simple approach for preparation of β-amino acids derivatives containing CHF₂, CBrF₂, and CClF₂ groups via addition reactions of the corresponding (Ss)-N-(tert-butanesulfinyl)-CXF₂-acetaldimines and alkyl-acetate-derived enolates. The reactions occur with excellent diastereoselectivity of up to >99:1 providing a simple and reliable access to a type of biologically valuable derivatives.

Detrifluoroacetylative generation of fluoro enolates is an emerging area of high-impact research. In this review article we provide, for the first time, a comprehensive and critical treatment of this subject. The reaction types reported to date include Mannich, aldol, and Michael addition and halogenation reactions. These processes can be very successfully conducted in asymmetric fashion, in stoichiometric or catalytic mode. In general, these reactions allow for synthetically rather simple and practical installation of CF₂, CHF, and quaternary CF structural units into various types of organic compounds. In particular, the overall scientific importance, as well as the potential influence of this methodology for the development of useful approaches to the preparation of pharmaceutically valuable compounds is highlighted. Attractive features such as operationally convenient, mild reaction conditions, remarkable substrate generality, and excellent stereochemical outcome bode well for widespread applications of this innovative and synthetically advanced approach.

A Cu-catalyzed asymmetric detrifluoroacetylative aldol addition reaction of 2-fluoro-1,3-diketones/hydrates to aldehydes in the presence of base and chiral bidentate ligand was developed. The reaction was carried out under convenient conditions and tolerated a wide range of substrates, resulting in fluorinated quaternary stereogenic α-fluoro-β-hydroxy ketone products with good chemical yields, diastereo- and enantioselectivities. This catalytic asymmetric detrifluoroacetylative aldol addition reaction provides a new approach for the preparation of biologically relevant products containing CF quaternary stereogenic centers.

A Cu-catalyzed asymmetric detrifluoroacetylative aldol addition reaction of 2-fluoro-1,3-diketones/hydrates to aldehydes in the presence of base and chiral bidentate ligand was developed. The reaction was carried out under convenient conditions and tolerated a wide range of substrates, resulting in fluorinated quaternary stereogenic α-fluoro-β-hydroxy ketone products with good chemical yields, diastereo- and enantioselectivities. This catalytic asymmetric detrifluoroacetylative aldol addition reaction provides a new approach for the preparation of biologically relevant products containing CF quaternary stereogenic centers.

A concise metal-free method for synthesizing 6-alkylthiophenanthridines from 2-isocyanobiaryls and disulfides proceeding through thiolation of isocyanides and intramolecular radical aromatic cyclization is reported. This process involves SS/C(sp²)H bond cleavage and CS/CC bond formation, which tolerates a wide range of substrates and gives good to excellent yields.

(S)-N-(tert-Butylsulfinyl)-3,3,3-trifluoroacetaldimine underwent reactions with enolates of glycine esters with quite remarkable stereochemical results, that is, with virtually complete (>99 % de) diastereoselectivity and excellent (>98 %) yields. Furthermore, the reactions are conducted under operationally convenient conditions (Cs₂CO₃-catalyzed, ambient temperature) to provide the most advanced, general, and scalable access to biologically important β-trifluoromethylated α,β-diamino acids.

This study describes the anomalous outcome of the Mannich-type reaction of N-tert-butylsulfinyl-3,3,3-trifluoroacetaldimine and Li derivatives of benzo[d]thiazoles, which offers a convenient and generalized method for the synthesis of biologically relevant (E)-1,2-bis(2-benzothiazolyl)ethanes. The mechanism, scope, and scalability of this new reaction are discussed.

The first direct asymmetric Mannich reaction of malononitrile to N-Boc-protected imines has been developed with cinchona alkaloid as catalyst. The procedure could tolerate a relatively wide range of substrates, and results in excellent yields and good enantioselectivities even in the presence of only 1 mol% of catalyst loading. The present work provides an easy access to β-amino malononitrile derivatives.

Tetrabenzylhafnium has been explored as a new organometallic reagent for the imine addition reaction. This reagent tolerates a wide scope of imines, affording α-branched amines in excellent yields without the use of any additive or catalyst. This new reagent shows higher efficiency than that observed for classic Grignard and organolithium reagents.