1042692-11-4

Basic information

• Product Name: (3S,4R)-methyl (Z)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate
• CAS NO: 1042692-11-4
• Molecular Weight: 213.233
• Mol File: 1042692-11-4.mol

Chemical Properties

• CAS DataBase Reference: (3S,4R)-methyl (Z)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate(CAS DataBase Reference)
• NIST Chemistry Reference: (3S,4R)-methyl (Z)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate(1042692-11-4)
• EPA Substance Registry System: (3S,4R)-methyl (Z)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate(1042692-11-4)

Safety Data

• Hazardous Substances Data: 1042692-11-4(Hazardous Substances Data)

Upstream product

• 95456-67-0 methyl (Z)-3-amino-2,3-dideoxy-4,5-O-isopropylidene-6-O-methylsulphonyl-D-erythro-hex-2-enonate 
• 90409-96-4 (3aR,4R,6aR)-2,2-dimethyl-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol 
• 95456-66-9 (2S,3R)-2,3-O-isopropylidene-4-O-methanesulfonylerythronitrile 
• 849480-74-6 (E/Z)-2,3-O-ispropylidene-D-erythrose-oxime 

Downstream Products

• 95456-64-7 (1S,5R,8R)-benzyl 8-hydroxy-3-oxo-2-oxa-6-azabicyclo<3.3.0>octane-6-carboxylate 
• 95456-65-8 (1R,5R)-(-)-6-aza-6-benzyloxycarbonyl-2-oxabicyclo[3.3.0]octan-3-one 
• 95456-63-6 (2R,3S,4R)-methyl (1-benzyloxycarbonyl-3,4-isopropylidenedioxypyrrolidin-2-yl)acetate 
• 115886-20-9 (3aR,6R,6aS)-6-(Imidazole-1-carbothioyloxy)-2-oxo-hexahydro-furo[3,2-b]pyrrole-4-carboxylic acid benzyl ester 

Relevant articles and documents

Enantiospecific Synthesis of (+)-Retronecine, (+)-Crotonecine, and Related Alkaloids

Reaction of 2,3-O-isopropylidene-D-ribose (8) with diallylzinc gave a triol, which on treatment with periodate was converted into 5,6,7-trideoxy-2,3-O-isopropylidene-L-ribo-hept-6-enofuranose (10) (86percent).Reaction with hydroxylamine hydrochloride in pyridine gave an oxime (11), which was treated with methanesulphonyl chloride in pyridine to yield 5,6,7-trideoxy-2,3-O-isopropylidene-4-O-methylsulphonyl-L-ribo-hept-6-enononitrile (12) (87percent overall).Reduction with lithium aluminium hydride and cyclisation followed by treatment with benzyl chloroformate gave (2R,3S,4R)-2-allyl-1-benzyloxycarbonyl-3,4-isopropylidenedioxypyrrolidine (14), which on oxidation and subsequent reaction with diazomethane yielded (2R,3S,4R)-methyl (1-benzyloxycarbonyl-3,4-isopropylidenedioxypyrrolidin-2-yl)acetate (15b) (35percent).A higher-yielding route to diester (15b) proceeded from 2,3-O-isopropylidene-D-erythrose (17), which was converted via its oxime into 2,3-O-isopropylidene-4-O-methylsulphonyl-D-erythrononitrile (19) (91percent).Reaction with methyl bromoacetate and activated zinc, followed by base-catalysed cyclisation, gave (3S,4R)-methyl (3,4-isopropylidenedioxypyrrolidin-2-ylidene)acetate (21) (78percent), which with cyanoborohydride followed by N-acylation produced compound (15b) (87percent).Treatment of diester (15b) with acid produced a γ-lactone (23), which was deoxygenated via its O-thiocarbonylimidazolide (24).Hydrogenolysis yielded (1R,5R)-2-oxa-6-azabicyclooctan-3-one hydrochloride (6) (69percent overall), which can be converted by known methods into (+)-retronecine (5) and other pyrrolizidine alkaloids. (1S,5R,8R)-ethyl 8-hydroxy-3-oxo-2-oxa-6-azabicyclooctane-6-carboxylate (28) was converted into its silyl ether (29), which underwent Dieckmann cyclisation to the pyrrolizidine (31), which is convertible by known methods into (+)-crotanecine (7).