Synthetic Approach toward Enantiopure Cyclic Sulfinamides

Abstract

A synthetic approach toward densely substituted enantiopure cyclic sulfinamides possessing up to four consecutive stereogenic centers was developed based on a completely diastereoselective S N 2′ cyclization/ tert -Bu cleavage sequence. Diastereospecific transformation of the obtained scaffold into chiral S VI derivatives such as sulfoximines and sulfonimidamides is demonstrated.

Recent advances in the synthesis of cyclic sulfinic acid derivatives (sultines and cyclic sulfinamides)

“…More recently, Suna and co-workers reported a new synthetic approach toward densely substituted enantiopure cyclic sulfinamides 85 based on a completely diastereoselective S N 2′ cyclization in the presence of base and de- tert -butylation sequence under mild silica gel acid conditions from sulfinamide derivatives 83 (Scheme 31). 41 The reaction scope was wide, including monoalkyls, dialkyls, aryls and heteroaryls with functional groups, such as iodide, bromo, double bond, and TIPS-protected hydroxyl, affording the desired cyclic sulfinamides 85 in moderate to high yields. The crystal structure was obtained and decisively confirmed the stereoretentive character of the products.…”

Cyclic Sulfinamides

“…Eventually, sp 3 -enriched γ-sultims 107 were obtained in fair to good yields over the two steps one-pot process (Scheme 44). [79] Worthy of note, that the target sultims not only possess up to 4 stereogenic centers but are also decorated with synthetically useful vinyl handle. However, the above method was applicable for the synthesis of γ-sultims only.…”

“…[147][148][149][150][151][152] There are some other ordinary examples of oxidation of γsultims with mCPBA. Interestingly, while sp 3 -enriched γ-sultims 96 a (prepared via Scheme 40) and 107 d (prepared via Scheme 44) were oxidized at rt, their bezofused congener 104 d (prepared via Scheme 43) required lower (0 °C) temperature (Scheme 92, A, [76] B, [79] and C [78] ). Under these conditions, the pyridine ring of γ-sultam 228 remained intact.…”

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

“…Polythiazyl (SN) x was first synthesized in 1906 and contains alternating sulfur and nitrogen atoms along its backbone (Figure ). − It has many interesting properties such as being one of only two examples of a synthetic polymer that is metallic at room temperature under atmospheric pressure and in the absence of doping. − This polymer is also superconducting with a critical temperature of 0.3 K. − Unfortunately, its straightforward composition does not lead to simple methods to alter its structure or properties, most research has described doping with different chemicals. − This polymer has been heavily investigated since its discovery, and different methods to synthesize it and its derivatives have been developed as well as numerous potential applications that take advantage of its electrical conductivity through the alternating sulfur–nitrogen bonds. − Unfortunately, its applications are limited due to its unstable nature that leads to degradation in water or under atmospheric conditions to give a gray powder. ,,,,, Although a large diversity of small organic compounds containing sulfur–nitrogen bonds have been studied for their biological activities ,− and synthesis of transition-metal complexes, − surprisingly few polymers possess nitrogen–sulfur bonds along the backbone. ,, We recently reported the synthesis of polysulfenamides, polydiaminosulfides, and polydiaminodisulfides, but these polymers possess sp 3 hybridized carbon atoms along their backbones that interrupt conjugation. ,,,…”