Regio- and Enantioselective Ring-Opening of Epoxides with HMDST: A Straightforward Access to 1,2-Mercaptoalcohols

Abstract

TBAF-catalyzed reaction of a range of substituted epoxides with hexamethyldisilathiane smoothly affords a direct and simple access to b-mercaptoalcohols in a highly regio-and stereoselective way.

Bis(trimethylsilyl)selenide in the Selective Synthesis of β‐Hydroxy, β‐Mercapto, and β‐Amino Diorganyl Diselenides and Selenides Through Ring Opening of Strained Heterocycles

“…20 %) ( Table 1, entry 9), as has previously been observed in the reaction of the analogue HMDST. [28] With the aim of evaluating the limits and the potential of this methodology, we extended this reactivity to different ring-strained compounds, such as thiiranes 4a-c and aziridines 6a-d, and 7a and 7b, obtained from natural amino acids: this investigation led to the development of a straightforward route to a variety of β-mercapto diselenides 5a-c (Scheme 2) and chiral N-tosyl-or N-Boc-protected β-amino diselenides 8a-d and 9a,b (Scheme 2) as single regioisomers, by following the S N 2 pathway exclusively. Examples of this reactivity are summarized in Table 1 (entries 15-17 and 18-23).…”

“…[27] More recently, we described the reaction of epoxides with HMDST, which afforded direct access to β-marcaptoalcohols in a regio-and stereoselective way. [28] On the other hand, the chemistry of the corresponding selenium derivative, bis(trimethylsilyl)selenide (TMS-Se-TMS, HMDSS) [29] has received less attention. It may be regarded as the synthetic equivalent of H 2 Se, but it is much easier to handle and to measure, and can be stored under inert atmosphere for months at low temperature, without appreciable decomposition.…”

Selective access to sulfurated and selenated heterocycles by intramolecular cyclization of β-substituted sulfides and selenides

“…Thus, β-mercapto alcohols 2, easily obtained through reaction of bis(trimethylsilyl)sulfide (HMDST) 1 and variously substituted epoxides 16 , were treated with bromo acetate (Scheme 1, X = O), in the presence of Cs 2 CO 3 /TBAI system 17 . Under these conditions, a clean S-alkylation occurred, leading to the corresponding δ-hydroxy-α-thioesters 3 in good yields.…”

A Remarkable Influence of a Trifluoromethyl Group on the Reactions of β‐Mercaptoalcohols with Fluorinated α‐Bromoenones

“…Starting Materials: Commercially available solvents and mercaptoethanol ( 11a ) were used. β‐Mercaptoalcohols 11b – 11d were synthesized in accordance with ref …”

“…1‐(Benzyloxy)‐3‐mercaptopropan‐2‐ol (11c): The product was obtained by following the reported procedure . Yield 562 mg (89 %).…”