134680-56-1

Upstream product

• 77144-67-3 DL-(1,3/2,4)-4-(hydroxymethyl)-5-cyclohexene-1,2,3-triol 
• 144677-80-5 Acetic acid (1R,2S,3R,4S,5S,6R)-2,3,4-triacetoxy-6-acetoxymethyl-5-bromo-cyclohexyl ester 
• 77144-65-1 DL-O-triacetyl-(1,3/2,4)-4-<(benzoyloxy)methyl>-5-cyclohexene-1,2,3-triol 
• 70838-35-6 DL-(1,3/2,4,6)-1,2,3-tri-O-acetyl-4-bromo-6-bromomethyl-1,2,3-cyclohexanetriol 

Downstream Products

• 77154-90-6 DL-hexa-O-acetyl-(1,3,4/2,5,6)-6-hydroxymethyl-1,2,3,4,5-cyclohexanepentol 
• 77144-69-5 DL-Penta-O-acetyl-(1,3,4/2,5,6)-5-azido-6-(hydroxymethyl)-1,2,3,4-cyclohexanetetrol 
• 77144-70-8 DL-Penta-O-acetyl-(1,3,4/2,5,6)-5-azetamido-6-(hydroxymethyl)-1,2,3,4-cyclohexanetetrol 
• 154287-16-8 (1S,2R,3S,4R,5R,6R)-2,3,4-Tris-(4-methoxy-benzyloxy)-5-(4-methoxy-benzyloxymethyl)-7-thia-bicyclo[4.1.0]heptane 

Relevant academic research and scientific papers

Vinylogy in orthoester hydrolysis: Total syntheses of cyclophellitol, valienamine, gabosine K, valienone, gabosine G, 1-epi-streptol, streptol, and uvamalol A

C7-cyclitols represent an important category of natural products possessing a broad spectrum of biological activities. As each member of these compounds is structurally unique, the usual practice is to synthesize them individually from appropriate polyhydroxylated chiral pools. We have observed an unusual vinylogy in acid mediated hydrolysis of enol ethers of myo-inositol 1,3,5-orthoesters giving a synthetically versatile polyhydroxylated cyclohexenal intermediate. We have exploited this unprecedented reaction for developing a general strategy for the rapid and efficient syntheses of several structurally diverse natural products of C7-cyclitol family. We have made an appropriately protected advanced intermediate 25 in five steps from the cheap and commercially available myo-inositol, and this common intermediate has been used to synthesize eight natural products in racemic form. We could synthesize (±)-cyclophellitol in seven steps, (±)-valienamine in five steps, (±)-gabosine I in five steps, (±)-gabosine G in six steps, (±)-gabosine K in three steps, (±)-streptol in six steps, (±)-1-epi-streptol in two steps, and (±)-uvamalol A in five steps from this intermediate.

Total syntheses of (±)-cyclophellitol and (1R°,6S°)-cyclophellitol

A stereodivergent synthesis of (+)-cyclophellitol (1) and its unnatural diastereoisomer (1R*6S*)-cyclophellitol (2), starting from the Diels-Alder adduct of furan and acrylic acid, is reported. The stereochemistry of the key step, the epoxidation of alkene 7, is controlled by the nature of the hydroxyl protecting groups.

A stereodivergent synthesis of (±)-cyclophellitol and (1R*,6S*)-cyclophellitol from the 7-oxabicyclo-[2.2.1]hept-5-ene-2-endo-carboxylic acid

A concise, stereodivergent synthesis of (±)-cyclophellitol 1 and its unnatural diastereoisomer (1R*,6S*)-cyclophellitol 2 starting from the Diels-Alder adduct of furan and acrylic acid is reported. The stereochemistry of the key step (the epoxidation of a

Total synthesis of cyclophellitol starting from furan

(±)-Cyclophellitol has been prepared in a highly stereoselective fashion from the Diels-Alder adduct of furan to 1-cyanovinyl acetate.

SYNTHESIS OF HEXA-N,O-ACETYL-DL-HYDROXYVALIDAMINE

DL-(1,3,4/2,5,6)-4-amino-6-hydroxymethyl-1,2,3,5-cyclohexanetetrol (DL-hydroxyvalidamine) was first synthesized as the peracetate, which confirmed the proposed structure of the branched-chain aminocyclitol derived by hydrogenolysis of antibiotic validamyc