Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

1,4‐Dithiane‐2,5‐diol: An Attractive Platform for the Synthesis of Sulfur‐Containing Functionalized Heterocycles

“…[1,2] In 1992, Effenberger and co-workers described an approach to 5-thio-D-xylulofuranoses 5 and 6 through the reaction between mercaptoacetaldehyde and dihydroxyacetone phosphate (3), catalyzed by rabbit muscle aldolase (RAMA); this was probably the first utilization of 1,4dithiane-2,5-diol (1) for the synthesis of a tetrahydrothiophene system. [1,2] In 1992, Effenberger and co-workers described an approach to 5-thio-D-xylulofuranoses 5 and 6 through the reaction between mercaptoacetaldehyde and dihydroxyacetone phosphate (3), catalyzed by rabbit muscle aldolase (RAMA); this was probably the first utilization of 1,4dithiane-2,5-diol (1) for the synthesis of a tetrahydrothiophene system.…”

“…[1,2] In relation to other starting materials, 1,4-dithiane-2,5-diol (1), the dimer of mercaptoacetaldehyde (2), has emerged as an attractive platform for the preparation of these frameworks (Scheme 1). [1,2] In relation to other starting materials, 1,4-dithiane-2,5-diol (1), the dimer of mercaptoacetaldehyde (2), has emerged as an attractive platform for the preparation of these frameworks (Scheme 1).…”

Organocatalytic asymmetric approach to spirocyclic tetrahydrothiophenes containing either a butenolide or an azlactone structural motif

“…[10][11][12][13][14][15][16][17][18][19][20][21][22][23] For instance, the tetrahydrothiophene structural motif is present in various natural products and pharmacologically active molecules (Figure 1, top). [10][11][12] 2(3H)-Furanones, commonly known as Δ β,γ -butenolides, are another group of biologically relevant molecules that has been successfully applied in the target-oriented organic synthesis (Figure 1, middle). [13][14][15][16][17][18] Furthermore, this group of unsaturated γ-lactones is also widely distributed in nature.…”

Organocatalytic Asymmetric Synthesis of Spiro‐Tetrahydrothiophene Oxindoles Bearing Four Contiguous Stereocenters by One‐Pot Michael–Henry‐Cascade–Rearrangement Reactions

“…[1a, 2] Among the various classes of organosulfur scaffolds, optically active polysubstituted tetrahydrothiophenesh ave attracted considerable attention in the past decades due to their broad prevalence in natural products and marketed drugs with al arge spectrum of biological activities. [3] In particular, chiral spiro-tetrahydrothiophene oxindole represents ap romising scaffold for drug discovery. [4] For the construction of chiral tetrahydrothiophenes [3,5] and spiro-tetrahydrothiophene oxindoles, [6] catalytic asymmetric sulfa-Michael/aldoland sulfa-Michael/Michaelcascade reactions between a,b-unsaturated compounds and mercaptoacetaldehyde analoguesh ave been reported.…”

“…[3] In particular, chiral spiro-tetrahydrothiophene oxindole represents ap romising scaffold for drug discovery. [4] For the construction of chiral tetrahydrothiophenes [3,5] and spiro-tetrahydrothiophene oxindoles, [6] catalytic asymmetric sulfa-Michael/aldoland sulfa-Michael/Michaelcascade reactions between a,b-unsaturated compounds and mercaptoacetaldehyde analoguesh ave been reported. However,c urrent asymmetric synthetic methods only led to the assembly of functionalized tetrahydrothiophenes with three consecutive stereogenic centers.…”