N−H and C−H Functionalization of Sulfoximine: Recent Advancement and Prospects

Abstract

Sulfoximine and its congeners are a versatile class of structural motifs widely found in a plethora of pharmaceutical compounds and crop protection industries due to their fascinating structural architecture. Former discoveries nicely demonstrates the synthetic routes of unmasked and various N-functionalized sulfoximines but recent efforts from the synthetic community have divulged the applicability of sulfoximine analogue as reusable and transformable DG (directing group) to fabricate multifunctionalized (Het)arenes and enhance the bioactivities. Considering the synthetic potentiality and great influence of this scaffold, we provide a summary of NÀ H/CÀ H functionalization strategies of sulfoximine and application (as a directing group) with special emphasis on the mechanistic underpinnings. Additionally, we also hoped that this comprehensive review article (up to midst of 2020) will be useful for synthetic researchers and medicinal chemists and will inspire for further novel chemical transformations in this arena.

Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation

“…Benzothiadiazine‐1‐oxides are conventionally synthesized from the corresponding 1,2‐disubstituted benzenes with the appropriate sulfur and nitrogen functionalities [2, 4] . On the other hand, transition‐metal‐catalyzed C−H aminations/amidations of sulfoximines have recently emerged as concise methods to access benzothiadiazine‐1‐oxides from readily available starting materials (Scheme 1a) [2c, 5–8] . Since the seminal work by Bolm on the Cp*Rh III ‐catalyzed (Cp*=pentamethylcyclopentadienyl) ortho ‐C−H amidation of sulfoximines with an oxycarbamate, [6a] cobalt‐, [6b] rhodium‐, [6c,d] and iridium‐catalyzed [6e] C−H amidation/amination reactions that enable the straightforward construction of benzothiadiazine‐1‐oxide derivatives have been developed by the groups of Bolm, Chen, and Dong.…”

Dual Photocatalysis for the Straightforward Coupling of Thiosugars and Arylsulfoximines: Towards Unprecedented Cyclic Heteroatomic Structures

“…1H NMR (300 MHz, CDCl 3 ) δ 8.38 (d, J = 7.4 Hz, 1H), 7.80 (d, J = 7.2 Hz, 1H), 7.54 (2 superposed triplets J = 7.4 Hz, 2H), 6.69 (t, J = 55. 4…”

“…[3] The post-functionalization of the nitrogen atom as well as the moieties attached to the sulfur atom have also received increasing attention. [4] Notably, if the starting material is a perfluoroalkylthioether, the profound modification of the electronic properties of the sulfur atom results in increased difficulty in preparing the corresponding sulfoximines. [5] Two decades after the seminal work of Yagupolskii, [5a] one of our group proposed a method for easy access to S-phenyl S-perfluoroalkyl NH-sulfoximines (Scheme 1, eq.…”

Photochemistry of N‐Phenyl Dibenzothiophene Sulfoximine†

“…the PhN: generated. The generation of azobenzene is strongly indicative of two possible pathways: one where PhN 1 is generated after S-N bond cleavage from excited singlet state of 1 which further undergoes intersystem crossing (ISC) to produce PhN 3 , or singlet excited 1 undergoes ISC to generate triplet 1 (1 3 ) that then undergoes S-N cleavage to generate PhN 3 .…”

“…Sulfoximines have recently regained popularity as an important functional group in drug discovery and medicinal chemistry (1)(2)(3)(4)(5)(6)(7). The functional group, when added to lead compounds for generating analogues, has shown to increase chemical and metabolic stability and improve solubility (1,2,5).…”