Aza-Payne rearrangement of α,α-disubstituted-aziridinemethanols

The aza-Payne rearrangement of activated N-Ts-α,α-disubstituted-aziridinemethanols, induced by NaOH in the mixed solvent tBuOH/H2O/THF (4:5:1) or NaH in a mixed solvent of THF/HMPA (10:1), as well as some N-Boc-α,α-disubstituted-aziridinemethanols with the latter reagent/solvent combination, provides the corresponding epoxides in up to 99% yield.

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(2S,3S)-3-Methylaziridin-2-yl(diphenyl)methanolC16H17NO[α]D20=+80.0 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-3-Methylaziridin-2-yl(dibutyl)methanolC12H25NO[α]D20=-10.5 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-3-Methylaziridin-2-yl(dibenzyl)methanolC18H21NO[α]D20=-23.2 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-3-Methylaziridin-2-yl(bis(4-methoxyphenyl))methanolC18H21NO3[α]D20=+58.7 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S)-Aziridin-2-yl(diphenyl)methanolC15H15NO[α]D20=-22.6 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S)

(2S)-Aziridin-2-yl(dibutyl)methanolC11H23NO[α]D20=-21.4 (c 10.0, THF)Source of chirality: asymmetric synthesisAbsolute configuration: (2S)

(2S)-Aziridin-2-yl(dibenzyl)methanolC17H19NO[α]D20=-28.4 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S)

(2S)-Aziridin-2-yl(bis(4-methoxyphenyl))methanolC17H19NO3[α]D20=+67.0 (c 9.0, THF)Source of chirality: asymmetric synthesisAbsolute configuration: (2S)

(2S,3S)-(3-Methyl-1-tosylaziridin-2-yl)diphenylmethanolC23H23NO3S[α]D20=+22.1 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-(3-Methyl-1-tosylaziridin-2-yl)dibutylmethanolC19H31NO3S[α]D20=-5.2 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-(3-Methyl-1-tosylaziridin-2-yl)dibenzylmethanolC25H27NO3S[α]D20=-58.5 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-(3-Methyl-1-tosylaziridin-2-yl)bis(4- methoxyphenyl)methanolC25H27NO5S[α]D20=+32.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(S)-(1-Tosylaziridin-2-yl)diphenylmethanolC22H21NO3S[α]D20=-35.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-(1-Tosylaziridin-2-yl)dibutylmethanolC18H29NO3S[α]D20=-24.1 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-(1-Tosylaziridin-2-yl)dibenzylmethanolC24H25NO3S[α]D20=-47.4 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(2R,3S)-N-(1-(3,3-Diphenyloxiran-2-yl)ethyl)-4-methylbenzenesulfonamideC23H23NO3S[α]D20=+130.7 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)

(2R,3S)-N-(1-(3,3-Dibutyloxiran-2-yl)ethyl)-4-methylbenzenesulfonamideC19H31NO3S[α]D20=+36.2 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)

(2R,3S)-N-(1-(3,3-Dibenzyloxiran-2-yl)ethyl)-4-methylbenzenesulfonamideC25H27NO3S[α]D20=-28.9 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)

(2R,3S)-N-(1-(3,3-Bis(4-methoxyphenyl)oxiran-2-yl)ethyl)-4-methylbenzenesulfonamideC25H27NO5S[α]D20=-26.2 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2R,3S)

(2R)-N-((3,3-Diphenyloxiran-2-yl)methyl)-4-methylbenzenesulfonamideC22H21NO3S[α]D20=+84.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(2R)-N-((3,3-Dibutyloxiran-2-yl)methyl)-4-methylbenzenesulfonamideC18H29NO3S[α]D20=+37.4 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(2R)-N-((3,3-Dibenzyloxiran-2-yl)methyl)-4-methylbenzenesulfonamideC24H25NO3S[α]D20=+40.5 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(2S,3S)-tert-Butyl 2-(hydroxydiphenylmethyl)-3-methylaziridine-1-carboxylateC21H25NO3[α]D20=-1.5 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2S,3S)-tert-Butyl 2-(hydroxybis(4-methoxyphenyl)-3-methylaziridine-1-carboxylateC23H29NO5[α]D20=-9.8 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (2S,3S)

(2R,3S)-tert-Butyl 1-(3,3-diphenyloxiran-2-yl)ethylcarbamateC21H25NO3[α]D20=+78.0 (c 1.0, CHCl3)Source of chirality: asymmetrical synthesisAbsolute configuration: (2R,3S)

(2R,3S)-tert-Butyl 1-(3,3-bis(4-methoxyphenyl)oxiran-2-yl)ethylcarbamateC23H29NO5[α]D20=+20.0 (c 0.6, CHCl3)Source of chirality: asymmetrical synthesisAbsolute configuration: (2R,3S)