β-Hydroxy sulfides and their syntheses

Abstract

Sulfur-containing natural products are ubiquitous in nature, their most abundant source being marine organisms since sulfur, in the form of the sulfate ion, is the second most abundant anion in sea water after chloride. As part of natural products, sulfur can appear in a multitude of combinations and oxidation states: thiol, sulfide (acyclic or heterocyclic), disulfide, sulfoxide, sulfonate, thioaminal, hemithioacetal, various thioesters, thiocarbamate and isothiocyanate. This review article focuses on β-hydroxy sulfides and analogs; their presence in natural products, general protocols for their synthesis, and examples of their application in target oriented synthesis.

Two New Cytotoxic Compounds from a Deep-Sea Penicillum citreonigrum XT20-134

“…Sulfur can appear in a multitude of combinations and oxidation states: thiol, sulfide, disulfide, sulfoxide, sulfonate, etc. The diversity of sulfur-containing chemical structures leads to their various bioactivities [29]. Among them, psammaplin A, has been found to have a broad bioactive spectrum, especially in terms of antimicrobial and antiproliferative activities [30].…”

Chemoenzymatic Cascades for the Enantioselective Synthesis of β‐Hydroxysulfides Bearing a Stereocentre at the C−O or C−S Bond by Ketoreductases

“…[9] Therefore, synthetic approaches towards their preparation have captured wide attention. [10] Classic routes to chiral β-hydroxysulfides include the asymmetric ring opening of epoxides [11] or cyclic carbonates [12] with thiophenols/mercaptanes catalysed by metal complexes based on chiral BINOL, [13] salen, [14] or bipyridine ligands. [15] However, these methods show some drawbacks such as the requirement of metals and complex chiral ligands, the usage of not easily accessible starting materials and, in some cases, unsatisfactory regio-and enantioselectivities.…”

“…In addition, chiral β‐hydroxysulfides are also useful building blocks in medicinal [8] and organic chemistry [9] . Therefore, synthetic approaches towards their preparation have captured wide attention [10] . Classic routes to chiral β‐hydroxysulfides include the asymmetric ring opening of epoxides [11] or cyclic carbonates [12] with thiophenols/mercaptanes catalysed by metal complexes based on chiral BINOL, [13] salen, [14] or bipyridine ligands [15] .…”

Intermolecular difunctionalization of alkenes: synthesis of β-hydroxy sulfides

“…Recently, Kinfe and co-workers highlighted this synthetic strategy in their interesting review paper entitled “β-hydroxy sulfides and their syntheses”. 9 However, several important examples were omitted and generally the explanation of mechanistic pathways of the reactions were ignored. In connection with our recent works on organosulfur chemistry 10 and modern organic synthesis, 11 herein we will attempt to provide a comprehensive overview of the synthesis of β-hydroxy sulfides through intermolecular difunctionalization of the respective alkenes with particular emphasize on the mechanistic aspect of reactions which may allow possible new insights into catalyst improvement.…”