Ring opening of chiral 2-(1-aminoalkyl)epoxides by aliphatic thiols with total selectivity: synthesis of enantiopure 3-amino-1-(alkylthio)alkan-2-ols

Highly Enantioselective Access to α‐Dibenzylamino Ketones from Chiral Nonracemic α‐Bromo α′‐Sulfinyl Ketones by Dynamic Kinetic Resolution: Synthesis of (2R,1′S)‐2‐[1‐(Dibenzylamino)alkyl]oxiranes

“…To illustrate the utility of the α‐( S )‐dibenzylamino α′‐( R )‐sulfinyl ketone intermediates, we planned to bring about their transformation into syn ‐(2 R ,1′ S )‐2‐[1‐(dibenzylamino)alkyl]epoxides (DBAE), which are very usefulmoieties in organic synthesis19 that have been used to prepare a large number of biologically active natural and synthetic compounds, such as hydroxyethylene dipeptide isosteres20 and other pharmacologically important compounds 21. Ring opening of DBAE with total regioselectivity by ketones,22a nitriles,22b,22c thiols,22d carboxylicacids,22e and organolithium compounds22f,22g was recently reported by Concellón and co‐workers. DBAE have also been used as precursors for the synthesis of oxazolidinones,23a 4‐(1‐dibenzylaminoalkyl)‐2‐oxo‐1,3‐dioxolanes,23b 2,5‐disubstituted‐1,4‐dioxanes with C 2 symmetry,23c and cis ‐ or trans ‐3,4‐disubstituted 1,2,3,4‐tetrahydroisoquinolines 23d…”

Catalytic ring-opening addition of thiols to epoxides in the gas-phase over molecular rhenium sulfide cluster complexes [Re6S8X6] (X=Cl, OH, H2O) with retention of their octahedral metal frameworks

“…In parallel with halide cluster catalysis, we have been studying catalysis by molybdenum [5,6] and Brønsted acid catalysts. Nonmetallic BF 3 OEt 2 [15] was used as a Lewis acid catalyst. Metals that can accept a lone pair of electrons have been used as Lewis acid catalysts; Zn(ClO 4 ) 2 [16], Er(OTf) 3 [17], LiClO 4 [18], InCl 3 [11,19], ReO 2 I(PPh 3 ) 2 [20], Ga complex [21], Ti-Ga-Salen [22] have been used as homogeneous catalysts.…”

Unusual Totally Selective Cyclodimerization of Epoxides: Synthesis of a Pair of Diastereoisomers of Enantiopure 2,5‐Disubstituted‐1,4‐Dioxanes with C2 Symmetry

“…[18] More recently, we described various transformations of these amino epoxides into a variety of enantiopure compounds, based on the highly regioselective nucleophilic opening of the oxirane ring. Thus, we reported the transformation of the oxirane ring into 1,3-dioxolanes, [19] 1,3-diaminoalkan-2-ols, [20] O 1 -acyl-3-aminoalkane-1,2-diols, [21] b-amino alcohols, [22] and 1-alkylthio-3-aminoalkan-2-ols [23] by reaction with ketones, nitriles, carboxylic acids, organolithium compounds or thiols, respectively.…”