| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1348108 | Tetrahedron: Asymmetry | 2012 | 7 Pages |
A library of pinane-based aminodiols were prepared from commercially available (1R)-(−)-myrtenol (−)-1. Compound (−)-1 was transformed into allyl trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl, and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (−)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (−)-15. The aminodiols and their oxazolidine derivatives 5–15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9.
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2,2,2-Trichloro-N-((1R,2R,3S,5R)-2-hydroxy-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-3-yl)acetamideC12H18Cl3NO3[α]D20=+18.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-ol hydrochlorideC10H20ClNO2[α]D20=-4.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC10H19NO2[α]D20=-11.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: 1R,2R,3S,5R
(1R,2R,3S,5R)-3-Isopropylamino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC13H25NO2[α]D20=+14.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Pentan-3-ylamino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC15H29NO2[α]D20=+5.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Cyclohexylamino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC16H29NO2[α]D20=+9.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Benzylamino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC17H25NO2[α]D20=+10.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-Dibenzylamino-2-hydroxy-methyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC24H31NO2[α]D20=+11.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
[(1R,2R,6S,8R)-5-Benzyl-9,9-dimethyl-3-oxa-5-azatricyclo[6.1.1.02,6]dec-2-yl]methanolC18H25NO2[α]D20=+3.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,6S,8R)
(1R,2R,3S,5R)-3-Benzyl(methyl)amino-2-hydroxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC18H27NO2[α]D20=+8.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-3-(N-Benzyl-N-methylamino)-2-benzyloxymethyl-6,6-dimethylbicyclo[3.1.1]heptan-2-olC25H33NO2[α]D20=+30.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
(1R,2R,3S,5R)-2-Hydroxymethyl-3-methylamino-6,6-dimethyl-bicyclo[3.1.1]heptan-2-olC11H21NO2[α]D20=+9.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: (1R,2R,3S,5R)
[(1R,2R,6S,8R)-5,9,9-Trimethyl-3-oxa-5-azatricyclo[6.1.1.02,6]dec-2-yl]methanolC12H21NO2[α]D20=-11.0 (c 0.125, MeOH)Source of chirality: (1R,5S)-myrtenolAbsolute configuration: 1R,2R,6S,8R
