| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1345466 | Tetrahedron: Asymmetry | 2015 | 10 Pages |
The synthesis of new homochiral l-prolinamido-sulfonamides 1–7 from enantiomerically pure (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthracene (R,R)-8 is reported. The l-prolinamido-sulfonamides 1–7 were tested as organocatalysts (10 mol %) in the aldol reaction of p-nitrobenzaldehyde and acetone in dichloromethane at room temperature in the presence of water (1 equiv) and acetic acid (20 mol %) giving good to high yields and enantioselectivities. Catalyst 4 (10 mol %) afforded the best results in the aldol reaction of acetone with p-substituted-benzaldehydes with electron withdrawing groups (i.e., nitro, cyano, bromo and chloro, up to 97% yield and 90% ee). The origin of the enantioselective induction was modeled using DFT methods. The estimated enantioselectivity for the model system is consistent with the experimental data.
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(R,R)-11-(4-Methylbenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC28H30N3O3S[α]D20 = −94.3 (c 1.1, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(4-Fluorobenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC27H27FN3O3S[α]D20 = −83.7(c 1.4, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(4-tert-Butylbenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC31H36N3O3S[α]D20 = −86.4 (c 1.5, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(4-Trifluoromethylbenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC28H27F3N3O3S[α]D20 = −79.8 (c 1.2, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(2,4,6-Triisopropylbenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC36H46N3O3S[α]D20 = −67.1 (c 1.0, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(2-Pyridinesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC26H27N4O3S[α]D20 = −74.2 (c 1.5, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-[(1S,2R)-(7,7-Dimethyl-2-hydroxybicyclo[2.2.1]hept-1-yl)methanesulfonamido]-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC31H40N3O4S[α]D20 = −60.1 (c 1.2, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,1S′,2R′S)
(R,R)-11-(2-Pyridinesulfonamido)-12-amino-9,10-dihydro-9,10-ethanoanthraceneC21H20N3O2S[α]D20 = −31.4 (c 1, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R)
(R,R)-11-(4-Methylbenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC33H38N3O5S[α]D20 = −109.7 (c 1.2, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(4-Fluorobenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC32H35FN3O5S[α]D20 = −106.1 (c 1.4, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
C36H44N3O5S(R,R)-11-(4-tert-Butylbenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthracene[α]D20 = −103.7(c 1.1, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(4-Trifluoromethylbenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC33H35F3N3O5S[α]D20 = −110.1(c 1.0, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(2,4,6-Triisopropylbenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC41H54N3O5S[α]D20 = −64.6 (c 1.1, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(2-Pyridinesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC31H35N4O5S[α]D20 = −100.3 (c 1.2, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-[(S)-(7,7-Dimethyl-2-oxobicyclo[2.2.1]hept-1-yl)methanesulfonamido]-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC36H46N3O6S[α]D20 = −57.8 (c 1.5, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S,S′)
(R,R)-11-(N-4-Trifluoromethylbenzenesulfonyl-N-methylamino)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxa-mido]-9,10-dihydro-9,10-ethanoanthraceneC34H37F3N3O5S[α]D20 = −76.3 (c 1.3, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(R,R)-11-(N-4-Trifluoromethylbenzenesulfonyl-N-methylamino)-12-[(S)-pyrrolidine-2-carboxa-mido]-9,10-dihydro-9,10-ethanoanthraceneC29H29F3N3O3S[α]D20 = −62.2 (c 1.0, CHCl3)Source of chirality: (R,R)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (R,R,S)
(S,S)-11-(4-Trifluoromethylbenzenesulfonamido)-12-[(S)-1-(tert-butoxycarbonyl)pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC33H35F3N3O5S[α]D20 = −4.5 (c 1, CHCl3)Source of chirality: (S,S)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (S,S,S)
(S,S)-11-(4-Trifluorobenzenesulfonamido)-12-[(S)-pyrrolidine-2-carboxamido]-9,10-dihydro-9,10-ethanoanthraceneC28H27F3N3O3S[α]D20 = +29.6 (c 1.2, CHCl3)Source of chirality: (S,S)-11,12-diamino-9,10-dihydro-9,10-ethanoanthraceneAbsolute configuration: (S,S,S)
