74645-52-6

Upstream product

• 70838-35-6 DL-(1,3/2,4,6)-1,2,3-tri-O-acetyl-4-bromo-6-bromomethyl-1,2,3-cyclohexanetriol 
• 77144-72-0 (1SR,3SR,6RS,8SR,9SR,10SR)-9,10-diacetoxy-3-phenyl-2,4-dioxabicyclo[4.4.0]dec-7-ene 
• 77144-65-1 DL-O-triacetyl-(1,3/2,4)-4-<(benzoyloxy)methyl>-5-cyclohexene-1,2,3-triol 
• 74615-52-4 DL-tri-O-acetyl-(1,3/2,6)-6-bromo-4-bromomethyl-4-cyclohexene-1,2,3-triol 
• 77144-73-1 5,7-O-benzylidene derivative of DL-3,4-di-O-acetyl-1,2-anhydro-(1,2,4,6/3,5)-1,2,3,4,5-pentahydroxy-6-hydroxymethylcyclohexane 
• 84851-94-5 DL-Di-O-acetyl-1,7-O-benzylidene-5-O-(methylsulfonyl)-(1,3,4/2,5,6)-4-azido-6-(hydroxymethyl)-1,2,3,5-cyclohexanetetrol 
• 84851-93-4 DL-2,3,-Di-O-acetyl-1,7-O-benzylidene-(1,3,4/2,5,6)-4-azido-6-(hydroxymethyl)-1,2,3,5-cyclohexanetetrol 
• 84851-95-6 DL-Di-O-acetyl-3,7-O-benzylidene-(1,3,6/2)-6-azido-4-(hydroxymethyl)-4-cyclohexene-1,2,3-triol 
• 77144-67-3 DL-(1,3/2,4)-4-(hydroxymethyl)-5-cyclohexene-1,2,3-triol 
• 81692-16-2 DL-tetra-O-acetyl-(1,3/2,4)-4-chloro-4-C-hydroxymethyl-5-cyclohexene-1,2,3-triol 
• 81692-15-1 Acetic acid (1S,2R,5S,6R)-5,6-diacetoxy-2-chloro-2-hydroxymethyl-cyclohex-3-enyl ester 
• 74708-35-3 DL-Tetra-O-acetyl-(1,3,6/2)-6-azido-4-(hydroxymethyl)-4-cyclohexene-1,2,3-triol 
• 74024-01-4 DL-(1,3/2)-1,2,3-tri-O-acetyl-4-methylene-5-cyclohexene-1,2,3-triol 
• 108-24-7 acetic anhydride 

Downstream Products

• 84270-00-8 N-((1S,4R,5S,6S)-4,5,6-Trihydroxy-3-hydroxymethyl-cyclohex-2-enyl)-acetamide 
• 117193-67-6 DL-(1,2,4,6/3,5)-1-acetamido-3-C-acetoxymethyl-2,4,5-tri-O-acetyl-3-bromo-2,4,5,6-cyclohexanetetrol 
• 117193-69-8 DL-(1,6/2,3,4,5)-6-acetamido-2-C-acetoxymethyl-1,2,3,4,5-penta-O-acetyl-1,2,3,4,5-cyclohexanepentol 
• 117193-69-8 DL-(1,3,5/2,4,6)-6-acetamido-2-C-acetoxymethyl-1,2,3,4,5-penta-O-acetyl-1,2,3,4,5-cyclohexanepentol 
• 117193-66-5 DL-(1,2,4/3,5,6)-5-acetamido-1-C-acetoxymethyl-2,3,4-tri-O-acetyl-6-bromo-1,2,3,4-cyclohexanetetrol 
• 1447971-22-3 (1S,2R,3S,4S,5S,6R)-6-acetamido-4-(acetoxymethyl)-5-chloro-4-hydroxycyclohexane-1,2,3-triyl triacetate 
• 1447971-23-4 (1S,2R,3S,4S,5S,6R)-6-acetamido-4-(acetoxymethyl)-5-iodo-4-hydroxycyclohexane-1,2,3-triyl triacetate 
• 1448147-54-3 (1S,2R,3S,4S,5S,6R)-6-acetamido-4-(acetoxymethyl)-5-bromo-4-hydroxycyclohexane-1,2,3-triyl triacetate 
• 117193-69-8 DL-(1,4/2,3,5,6)-6-acetamido-2-C-acetoxymethyl-1,2,3,4,5-penta-O-acetyl-1,2,3,4,5-cyclohexanepentol 
• 38231-86-6 valienamine 

Relevant academic research and scientific papers

A flexible strategy based on a C2-symmetric pool of chiral substrates: Concise synthesis of (+)-valienamine, key intermediate of (+)- pancratistatin, and conduramines A-1 and E

A new strategy invoking a new application of the [3,3] sigmatropic rearrangement of allylic azides and the presence of a C2 symmetry element within a pool of chiral substrates was evolved. Not only does this simple flexible strategy provide a concise approach to (+)-valienamine, but it also can readily be adopted for the synthesis of conduramines A-1 and E and the enantiopure azido carbonate 4, a key intermediate of (+)-pancratistatin.

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.

Diastereospecific epoxidation and highly regioselective ring-opening of (+)-valienamine: Practical synthesis of (+)-valiolamine

An efficient and practical synthesis of (+)-valiolamine starting from readily available aminocyclitol (+)-valienamine in five steps and up to 80% total yield in gram-scale quantities is reported. Diastereospecific epoxidation by means of substrate directable reaction and regioselective ring-opening of corresponding epoxide are the key reactions in the synthesis, which circumvent laborious purification of products using chromatographical separation. The detailed mechanisms of epoxidation and ring-opening attacked by halide, including the directing and steric hindrance effect, are also discussed.

Lewis basic ionic liquid as an efficient and facile catalyst for acetylation of alcohols, phenols, and amines under solvent-free conditions

The Lewis basic ionic liquid 1,8-diazabicyclo[5.4.0]undec-7-en-8-ium acetate was employed for the acetylation of various phenols, alcohols, and amines in good-to-excellent yields at 50 C under solvent-free conditions in a short time. Compared with existing methods based on conventional catalysts and toxic solvents, the reported method is simple, mild and environmentally viable. Furthermore, the ionic liquid was conveniently separated from the products and easily recycled to catalyze other acetylation reactions with excellent yields. .

A C2-symmetric pool based flexible strategy: An enantioconvergent synthesis of (+)-valiolamine and (+)-valienamine

A new enantioconvergent strategy directed toward the synthesis of glucosidase inhibitors was developed by using a C2-symmetric element within the chiral pool and by applying an iodine-promoted cyclization of an unsaturated carbonimidothioate for the regio- and diastereocontrolled installation of amino and hydroxy units. Not only does this simple flexible strategy provide a convergent concise approach to (+)-valiolamine (1), but it can also be readily adopted for the synthesis of (+)-valienamine (2). Commercially available and cheap C2-symmetric D-tartaric acid served as the chiral building block. Copyright

A concise synthetic approach to (+)-valienamine starting from Garner's aldehyde

A synthesis of (+)-valienamine was achieved starting from Garner's aldehyde in ten steps and 23% overall yield. A unique feature of the synthetic route is that an acyclic precursor was constructed, using diastereoselective antireductive coupling reaction of alkyne and Garner's aldehyde as the key step, which was then cyclized in an intramolecular aldol reaction to form the valienamine skeleton. Georg Thieme Verlag Stuttgart · New York.

Stereoselective total synthesis of (+)-valienamine and (+)-4-epi- valienamine via a ring-closing enyne metathesis protocol

Stereoselective total synthesis of (+)-valienamine is reported utilizing Sharpless asymmetric dihydroxylation, diastereoselective Carreira alkynylation, and ring-closing enyne metathesis (RCEYM) as key steps from L-serine. A similar strategy is also reported for the first total synthesis of (+)-4-epi- valienamine. Georg Thieme Verlag Stuttgart.

Carbasaccharides via ring-closing alkene metathesis. A synthesis of (+)- valienamine from D-glucose

(+)-Valienamine (16) was prepared in seven steps and in an overall yield of 17% from commercially available 2,3,4,6-tetra-O-benzyl-D-glucopyranose. Stereoselective addition of vinylmagnesium bromide to the 1,3,4,5-tetra-O- benzyl-6,7-dideoxy-L-xylo-hept-6-en-2-ulose (2) gave diene 3 (86%). Ring- closing alkene metathesis of 3 in the presence of 0.15 equiv, of Grubb's catalyst 1 gave the cyclohexene 4 (58%), that was converted into (+)- valienamine (16) in three steps and in 47% yield. Similarly, ring-closing alkene metathesis of the D-mannose-derived diene 20 gave the cyclohexene 21 (89%).

Enantiospecific syntheses of valienamine and 2-epi-valienamine

Cyclic sulfite 10, readily available from (-)-quinic acid (3) in 10 steps, was ring opened regio- and stereospecifically with azide anion to give (1S,2R,3R,4R)-1-azido-3,4-di-O-benzyl-5-(benzyloxymethyl)cyclohex-5-ene- 2,3,4-triol (11). Deprotection of 11 afforded, for the first time, 2- epivalienamine (2), which was isolated as penta-N,O-acetyl-2-epi-valienamine (14). The configuration of the free hydroxy group in 11 was inverted by a two-step sequence to give the blocked valienamine 19 that was deprotected to give valienamine (1), isolated as penta-N,O-acetylvalienamine (21). This approach furnished (+)-valienamine (1) in 16 steps (7% overall yield) and recorded the first synthesis of 2-epi-valienamine (2) in 13 steps (11% overall yield).