95456-64-7

Upstream product

• 129570-51-0 (2R,3S)-1-benzyloxycarbonylamino-4-pentene-2,3-diol 
• 13463-40-6 iron pentacarbonyl 
• 95456-67-0 methyl (Z)-3-amino-2,3-dideoxy-4,5-O-isopropylidene-6-O-methylsulphonyl-D-erythro-hex-2-enonate 
• 95456-67-0 methyl (E)-3-amino-2,3-dideoxy-4,5-O-isopropylidene-6-O-methylsulphonyl-D-erythro-hex-2-enonate 
• 1042692-11-4 (3S,4R)-methyl (Z)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate 
• 95456-61-4 (3S,4R)-methyl (E)-(3,4-O-isopropylidenedioxypyrrolidin-2-ylidene)acetate 
• 95456-62-5 (2R,3S,4R)-methyl (3,4-O-isopropylidenedioxypyrrolidin-2-yl)acetate 
• 95456-63-6 (2R,3S,4R)-methyl (1-benzyloxycarbonyl-3,4-isopropylidenedioxypyrrolidin-2-yl)acetate 
• 201230-82-2 carbon monoxide 

Downstream Products

• 687992-26-3 1,4,5-trideoxy-1,4-imino-D-lyxo-hexitol 
• 115886-20-9 (3aR,6R,6aS)-6-(Imidazole-1-carbothioyloxy)-2-oxo-hexahydro-furo[3,2-b]pyrrole-4-carboxylic acid benzyl ester 
• 95456-65-8 (1R,5R)-(-)-6-aza-6-benzyloxycarbonyl-2-oxabicyclo[3.3.0]octan-3-one 
• 129570-47-4 N-benzyloxycarbonyl-1,4,5-trideoxy-1,4-imino-D-lyxo-hexitol 

Relevant academic research and scientific papers

Continuous Pd-Catalyzed Carbonylative Cyclization Using Iron Pentacarbonyl as a CO Source

This work discloses a continuous flow carbonylation reaction using iron pentacarbonyl as source of CO. The described transformation using this surrogate was designed for use in commonly accessible flow equipment. Optimized conditions were applied to a sca

Homogeneous cyclocarbonylation of alkenols with iron pentacarbonyl

We report substantially improved reaction conditions for palladium(II)-catalyzed tandem cyclization-intramolecular oxycarbonylation of (amino)polyols with a terminal double bond, based on utilization of iron pentacarbonyl [Fe(CO)5] as an affordable and safe liquid supply of the carbonyl unit fully replacing gaseous carbon monoxide. Direct comparison with the classical version on a series of previously published substrates illustrates invariably shorter reaction times but comparable yields and selectivity. Georg Thieme Verlag Stuttgart · New York.

Halocyclization and palladium(II)-catalyzed amidocarbonylation of unsaturated aminopolyols. Synthesis of 1,4-iminoglycitols as potential glycosidase inhibitors

Syntheses of optically active 2,5-anhydro-1,4-dideoxy-1,4-iminoΔ- lyxitol (6), 1,4,5-trideoxy-1,4-imino-Δ-lyxo-hexitol (14), and its N-methyl derivative 15 from achiral divinylcarbinol, via the aminopentenediol 1, are described using halogen-promoted cyclization and Pd(II)-catalyzed amidocarbonylation as key steps. 2,5,6-Trideoxy-2,5-imino-Λ-ido-heptitol (23), a diastereomeric homologue of the naturally occurring pyrrolidine DMDP G, is prepared from Δ-glucosamine hydrochloride in 7 steps in 19% overall yield. The new compounds 6, 14,15, and 23 show weak glycosidase inhibition in two cases.

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).