tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

Abstract

The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.

Two Decades of Progress in the Asymmetric Intramolecular aza‐Michael Reaction

“…In this scenario, examples that employ N-sulfinyl amines with a dual role, as nitrogen nucleophiles and as chiral inducers, are becoming popular. [87] As we mentioned before, one of the main challenges associated with the asymmetric IMAMR is the generation of starting materials, where the nitrogen nucleophile and the Michael acceptor should coexist unreacted. One of the strategies employed to address this issue involved the use of nitrogen sources with attenuated nucleophilicity such as carbamates, sulfonamides and amides.…”

Desymmetrization of Cyclohexadienones through Phase-Transfer-Catalyzed Stereoselective Intramolecular Aza-Michael Addition with Chiral Sulfinamide Nucleophiles

“…R f = 0.31 [EtOAc:hexanes, 1:1 (v/v)]. 1 H NMR (CDCl 3 , 400 MHz) δ 8.06 (t, J = 3.9 Hz, 1H), 6.78−6.75 (m, 2H), 6.31−6.28 (m, 2H), 3.63−3.60 (m, 2H), 2.74−2.72 (m, 2H), 1.39 (s, 3H), 1.19 (s, 9H). 13 General Procedure B for the Synthesis of Substrate 1.…”

“…R f = 0.30 [EtOAc:hexanes, 2:1 (v/v)]. 1 H NMR (CDCl 3 , 400 MHz) δ: 6.79−6.70 (m, 2H), 6.37−6.34 (m, 2H), 3.59−3.58 (m, 1H), 3.55−3.50 (m, 1H), 3.45−3.31 (m, 2H), 3.24−3.18 (m, 1H), 1.78 (q, J = 7.6 Hz, 2H), 1.22 (s, 9H), 0.83 (t, J = 7.6 Hz, 3H). 13 (…”

“…T he use of asymmetric reactions involving chiral tert-butyl sulfinamides (Ellman's reagents) as auxiliaries is a reliable synthetic strategy for producing enantioenriched nitrogencontaining compounds such as chiral amines. 1,2 These reactions have been extended to the synthesis of numerous biologically crucial chiral cyclic compounds. 3,4 For example, Fustero and del Pozo described the use of tethered chiral tertbutyl sulfinamides as nucleophiles in stereoselective intramolecular aza-Michael reactions, which produced various nitrogen-containing heterocycles with excellent stereocontrol (Scheme 1a).…”

Transition metal-catalyzed reactions of N-sulfinyl imines

“…Chiral N-sulfinyl imines are important starting materials in asymmetric synthesis because in the reaction with carbon nucleophiles a new carbon-carbon bond is formed and a new stereocenter is generated [1]. As nucleophiles mainly organometallic reagents have been used, such as organoalkaline, organomagnesium, organozinc, organoboron, organoaluminium, organoindium and organosilicon compounds [2].…”