The catalyst 1-[(3R,4S)-1-benzyl-4-phenyl-pyrrolidin-3-yl]-3-[3,5-bis(trifluoromethyl)phenyl]urea (8) designed based on 1-[(3R)-1-benzylpyrrolidin-3-yl]-3-[3,5-bis(trifluoromethyl)phenyl]thiourea (4) and 1,3-bis[(3R,4S)-1-benzyl-4-phenylpyrrolidin-3-yl]urea (7) exhibited potent catalytic activity for the asymmetric Michael addition of thiols to β-nitrostyrenes. A mere 2 mol % of the catalyst afforded 2-nitro-1-phenylethylsulfides in high yields of up to 93% ee.

Double Michael addition of dithiols such as 1,3-propanedithiol and 1,2-ethanedithiol to α,β-acetylenic carbonyl compounds in the presence of molecular sieve and dimethyl sulfoxide proceeds very smoothly to afford the corresponding β-keto 1,3-dithianes and β-keto 1,3-dithiolanes, respectively, in good to high yields.Double Michael addition of 1,3-propanedithiol to α,β-acetylenic carbonyl compounds in the presence of molecular sieve and dimethyl sulfoxide proceeds very smoothly to afford the corresponding β-keto 1,3-dithianes in high yields.

A highly efficient and good enantioselective organocatalytic asymmetric acylation of racemic primary alcohols with acyl chlorides has been achieved catalyzed by a chiral 1,2-diamine derived from (S)-proline.(S)-1-Methyl-2-[(benzylmethylamino)methyl]pyrrolidineC14H22N2Ee = 100%[α]D = −83.0 (c 1.0, EtOH)Source of chirality: (S)-prolineAbsolute configuration: S(R)-4-Benzoyloxymethyl-2,2-dimethyl-1,3-dioxolaneC13H16O4Ee = 56%[α]D = +4.0 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R4-Benzoyloxymethyl-2,2-di-n-propyl-1,3-dioxolaneC17H24O4Ee = 60%[α]D = +11.9 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine4-Benzoyloxymethyl-2,2-di-n-butyl-1,3-dioxolaneC19H28O4Ee = 54%[α]D = +10.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(R)-2-Benzoyloxymethyl-1,4-dioxa-spiro[4.5]decaneC16H20O4Ee = 53%[α]D = +6.5 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: 2R(R)-4-Benzoyloxymethyl-2,2-diisopropyl-1,3-dioxolaneC17H24O4Ee = 59%[α]D = +8.9 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R4-Benzoyloxymethyl-2,2-dicyclohexyl-1,3-dioxolaneC23H32O4Ee = 51%[α]D = +7.5 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine4-Benzoyloxymethyl-2,2-dibenzyl-1,3-dioxolaneC25H24O4Ee = 23%[α]D = +1.0 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(R)-4-Benzoyloxymethyl-2,2-diphenyl-1,3-dioxolaneC23H20O4Ee = 54%[α]D = +16.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(o-Toluoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC18H26O4Ee = 61%[α]D = +6.1 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(m-Toluoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC18H26O4Ee = 51%[α]D = +8.6 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(p-Toluoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC18H26O4Ee = 68%[α]D = +10.4 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(p-t-Butylbenzoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC21H32O4Ee = 57%[α]D = +7.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(p-Methoxybenzoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC18H26O5Ee = 70%[α]D = +9.6 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-(p-Chlorobenzoyl)oxymethyl-2,2-diisopropyl-1,3-dioxolaneC17H23ClO4Ee = 51%[α]D = +5.4 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-4-α-Naphthoyloxymethyl-2,2-diisopropyl-1,3-dioxolaneC21H26O4Ee = 81%[α]D = +5.9 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration:R(R)-4-β-Naphthoyloxymethyl-2,2-diisopropyl-1,3-dioxolaneC21H26O4Ee = 78%[α]D = +10.3 (c 1.2, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-2-(α-Naphthoyloxymethyl)oxiraneC14H12O3Ee = 64%[α]D = −18.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: Rp-ToluoyloxyethyloxiraneC12H14O3Ee = 11%[α]D = −6.6 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(2S,3S)-2-(4-t-Butylbenzoyloxymethyl)-3-phenyloxiraneC20H22O3Ee = 44%[α]D = −13.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: 2S,3S(2S,3S)-2-Benzoyloxymethyl-2-methyl-3-phenyloxiraneC17H16O3Ee = 43%[α]D = −11.8 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: 2S,3S(R)-2-Benzoyloxymethyl-1- tosylaziridineC17H17NO4SEe = 32%[α]D = −8.2 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R2-(p-Toluoyloxymethyl)tetrahydrofuranC13H16O3Ee = 50%[α]D = −13.3 (c 1.2, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine2-(p-Toluoyloxymethyl)tetrahydropyranC14H18O3Ee = 41%[α]D = −1.3 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(R)-(2,2-Dimethyl-[1,3]dioxolan-4-yl)methanolC6H12O3Ee = 69%[α]D = −6.6 (c 1.3, MeOH)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(2,2-Di-n-propyl-[1,3]dioxolan-4-yl)methanolC10H20O3Ee = 64%[α]D = −3.3 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(2,2-Di-n-butyl-[1,3]dioxolan-4-yl)methanolC12H24O3Ee = 71%[α]D = −3.2 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(R)-(1,4-Dioxa-spiro[4.5]dec-2-yl)methanolC9H16O3Ee = 65%[α]D = −3.8 (c 0.1, MeOH)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(R)-(2,2-Diisopropyl-[1,3]dioxolan-4-yl)methanolC10H20O3Ee = 75%[α]D = −13.7 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(2,2-Dicyclohexyl-[1,3]dioxolan-4-yl)methanolC16H28O3Ee = 82%[α]D = −5.9 (c 1.1, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(2,2-Dibenzyl-[1,3]dioxolan-4-yl)methanolC18H20O3Ee = 29%[α]D = −2.4 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine(R)-(2,2-Diphenyl-[1,3]dioxolan-4-yl)methanolC16H16O3Ee = 62%[α]D = −24.5 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: R(2R,3R)-trans-3-PhenylglycidolC9H10O2Ee = 47%[α]D = +24.1 (c 1.8, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: 2R,3R(2R,3R)-trans-2-Methyl-3-phenylglycidolC10H12O2Ee = 48%[α]D = +9.1 (c 1.8, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: 2R,3R(S)-1-Tosylaziridine-2-methanolC10H13NO3SEe = 32%[α]D = −10.9 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: S(S)-t-ButyldiphenylsilyloxymethyloxiraneC19H24O2SiEe = 46%[α]D = −1.4 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamineAbsolute configuration: St-ButyldiphenylsilyloxyethyloxiraneC20H26O2SiEe = 12%[α]D = +1.6 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine2-(t-Butyldiphenylsilyloxymethyl)tetrahydrofuranC21H28O2SiEe = 46%[α]D = +2.6 (c 1.4, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine2-(t-Butyldiphenylsilyloxymethyl)tetrahydropyranC22H30O2SiEe = 41%[α]D = −3.0 (c 1.0, CHCl3)Source of chirality: asymmetric acylation catalyzed by chiral 1,2-diamine

Reaction of alcohols with tert-butyldimethylsilyl chloride in DMSO–hexane provides the corresponding tert-butyldimethylsilyl ethers in high yields under mild reaction conditions. This convenient reaction proceeds very smoothly at room temperature without a catalyst. Additionally, alcohols having an allylic alcohol, cyclopropane, and tetrahydrofuran moiety underwent chemoselective silylation to give the TBS ethers in good yields with no undesired reactions.