A new stereoselective approach to aminocyclohexitols using RCM

A new stereoselective approach for the synthesis of carbamannopyranosylamine and epi-valiolamine by using stereoselective allylation on lactamine and RCM from d-ribose has been described.

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(R)-1-((4R,5S)-5-((S)-1-(Benzylamino)but-3-enyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-(tert-butyldimethylsilyloxy)ethanolC24H41NO4Si[α]D25=+11.5 (c 1.9, CHCl3)Source of chirality: d-riboseAbsolute configuration: (R,4R,5S,S)

(S)-N-Benzyl-1-((4S,5S)-5-((R)-3,3-diethyl-8,8,9,9-tetramethyl-4,7-dioxa-3,8-disiladecan-5-yl)-2,2-dimethyl-1,3-dioxolan-4-yl)but-3-en-1-amineC30H55NO4Si2[α]D25=+24.1 (c 2.4, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5S,R)

Benzyl benzyl((S)-1-((4S,5S)-5-((R)-1-(3-ethylpentan-3-yloxy)-2-(2,3,3-trimethylbutan-2-yloxy)ethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)but-3-enyl)carbamateC38H61NO6Si2[α]D25=+5.4 (c 0.2, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5S,R)

Benzyl benzyl((S)-1-((4S,5S)-5-((R)-3,3-diethyl-8,8,9,9-tetramethyl-4,7-dioxa-3,8-disiladecan-5-yl)-2,2-dimethyl-1,3-dioxolan-4-yl)-4-hydroxybutyl)carbamateC38H63NO7Si2[α]D25=-32.5 (c 1.8, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5S,R)

Benzyl benzyl((S)-1-((4S,5S)-5-((R)-3,3-diethyl-8,8,9,9-tetramethyl-4,7-dioxa-3,8-disiladecan-5-yl)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-(hydroxymethyl)but-3-enyl)carbamateC39H63NO7Si2[α]D25=-21.1 (c 2.4, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5S,R)

Benzyl benzyl((S)-1-((4S,5S)-5-((R)-3,3-diethyl-8,8,9,9-tetramethyl-4,7-dioxa-3,8-disiladecan-5-yl)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-((methoxymethoxy)methyl)but-3-enyl)carbamateC41H67NO8Si2[α]D25=-19.9 (c 1.6, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5S,R)

Benzyl benzyl((S)-1-((4S,5R)-5-((R)-1,2-dihydroxyethyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-((methoxymethoxy)methyl)but-3-enyl)carbamateC29H39NO8[α]D25=+1.0 (c 1.9, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5R,R)

Benzyl benzyl((S)-1-((4S,5R)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)-3-((methoxymethoxy)methyl)but-3-enyl)carbamateC29H37NO6[α]D25=+13.7 (c 1.8, CHCl3)Source of chirality: d-riboseAbsolute configuration: (S,4S,5R)

Benzyl benzyl((3aS,4S,7aR)-6-((methoxymethoxy)methyl)-2,2-dimethyl-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxol-4-yl)carbamateC27H33NO6[α]D25=-23.2 (c 0.5, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,4S,7aR)

Benzyl benzyl((3aS,4S,7S,7aR)-7-hydroxy-6-((methoxymethoxy)methyl)-2,2-dimethyl-hexahydrobenzo[d][1,3]dioxol-4-yl)carbamateC27H35NO7[α]D25=-32.5 (c 1.8, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,4S,7S,7aR)

Benzyl benzyl((3aS,4S,6R,7R,7aR)-6,7-dihydroxy-6-((methoxymethoxy)methyl)-2,2-dimethyl-hexahydrobenzo[d][1,3]dioxol-4-yl)carbamateC27H35NO8[α]D25=-4.7 (c 1.3, CHCl3)Source of chirality: d-riboseAbsolute configuration: (3aS,4S 6R,7R,7aR)

(1S,2R,3S,4S)-4-Acetamido-6-(acetoxymethyl)cyclohexane-1,2,3-triyl triacetateC17H25NO9[α]D25=-14.7 (c 0.5, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1S,2R,3S,4S)

(1S,2S,3R,4R,6S)-6-Acetamido-4-(acetoxymethyl)-4-hydroxycyclohexane-1,2,3-triyl triacetateC17H26NO10[α]D25=+19.6 (c 0.6, CHCl3)Source of chirality: d-riboseAbsolute configuration: (1S,2S,3R,4R,6S)