863396-18-3

Upstream product

• 18162-48-6 tert-butyldimethylsilyl chloride 
• 98-59-9 p-toluenesulfonyl chloride 
• 261157-01-1 methyl N-toluenesulfonyl-O-t-butyldimethylsilyl-4-hydroxyprolinate 
• 51-35-4 4R-4-hydroxyproline 
• 16257-57-1 methyl (2S,4R)-4-hydroxy-1-(p-tolylsulfonyl)pyrrolidine-2-carboxylate 
• 40216-83-9 L-4-hydroxyproline methyl ester hydrochloride 
• 261157-02-2 (2S,4R)-1-(4-methylphenyl)sulfonyl-2-hydroxymethyl-4-(t-butyldimethylsilanyloxy)pyrrolidine 

Downstream Products

• 646039-38-5 [(2S,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-1-(toluene-4-sulfonyl)-pyrrolidin-2-yl]-(4-methoxy-phenyl)-methanol 
• 863396-16-1 (2S,4R)-1-(4-methylphenylsulfonyl)-2-vinyl-4-(t-butyldimethylsilyloxy)pyrrolidine 
• 1130814-63-9 2-(1-hydroxy-2-propenyl)-4-(t-butyldimethylsilanyloxy)-1-(4-methylphenylsulfonyl)-pyrrolidine 
• 1130814-77-5 2-(1-hydroxy-2-propenyl)-4-(t-butyldimethylsilanyloxy)-1-(4-methylphenylsulfonyl)-pyrrolidine 
• 261156-88-1 C₁₅H₂₈NO₃SiC₃H₅C₅H₈O₂H₂OSO₂C₇H₆ 
• 261156-91-6 (Diethoxy-phosphoryl)-acetic acid (1S,6R,7R)-8-oxo-9-phenylselanyl-2-aza-tricyclo[5.3.1.0^2,6]undec-7-yl ester 
• 261156-84-7 C₁₅H₂₉NO₃SiCOC₆H₅N 
• 261156-82-5 C₁₄H₁₇NO₄SSiC₆H₁₄C₂H₄O 
• 261157-03-3 3-[(2R,4R)-4-(tert-Butyl-dimethyl-silanyloxy)-1-(toluene-4-sulfonyl)-pyrrolidin-2-yl]-propionitrile 
• 261157-05-5 (1R,5R)-1-(tert-Butyl-dimethyl-silanyloxy)-6-(toluene-4-sulfonyl)-6-aza-bicyclo[3.2.1]octan-2-one 
• 261156-96-1 (1S,5R,7R,8R)-8-Hydroxy-5-methoxy-10-phenylselanyl-2-aza-tricyclo[6.3.1.0^2,7]dodec-10-en-9-one 
• 261157-00-0 C₁₈H₁₉NO₂Se 
• 261156-99-4 (1S,6R,7R)-7-Hydroxy-9-phenylselanyl-2-aza-tricyclo[5.3.1.0^2,6]undecan-8-one 
• 261157-04-4 3-[(2R,4R)-4-Hydroxy-1-(toluene-4-sulfonyl)-pyrrolidin-2-yl]-propionitrile 

Relevant academic research and scientific papers

Synthesis of N-tosylhomosphinganine and N-tosylsedridine

A straightforward synthesis of N-tosylhomosphinganine and N-tosylsedridine has been achieved from trans-4-hydroxyproline by Grignard addition, regioselective Baeyer-Villiger reaction, cross or ring-closing metathesis and hydrogenation as the key steps.

Formal syntheses of (-)- and (+)-aphanorphine from (2S,4R)-4-hydroxyproline

We describe the efficient formal syntheses of both natural (-)-aphanorphine and unnatural (+)-aphanorphine from the same commercially available amino acid, (2S,4R)-4-hydroxyproline. The tricyclic framework was constructed by intramolecular Friedel-Crafts

Synthesis of α-conhydrine

A synthesis of α-conhydrine has been achieved from trans-(2S,4R)-4-hydroxyproline via diastereoselective Grignard addition, regioselective Baeyer-Villiger reaction, and ring-closing metathesis as the key steps.

Synthesis of streptorubin B core

A straightforward synthesis of streptorubin B core structure has been established starting from trans-4-hydroxyproline. The core structure of streptorubin B is constructed in an intramolecular ring-closing metathesis as the key step.

Formal synthesis of epibatidine

A straightforward formal synthesis of epibatidine has been established starting from trans-(2S,4R)-4-hydroxyproline.

An Efficient Synthesis of (1R,4S)-1-Methyl-8-methoxy-3-(4-toluenesulfonyl)- 2,3,4,5-tetrahydro-1,4-methano-3-benzazepine. A Formal Synthesis of (-)-Aphanorphine

We report a highly efficient synthesis of (1R,4S)-1-methyl-8-methoxy-3-(4- toluenesulfonyl)-2,3,4,5-tetrahydro-1,4-methano-3-benzazepine in six steps from 5. The present work constitutes a new formal synthesis of marine alkaloid (-)-aphanorphine.

Total syntheses of the Securinega alkaloids (+)-14,15-dihydronorsecurinine, (-)-norsecurinine, and phyllanthine

A new strategy for enantiospecific construction of the Securinega alkaloids has been developed and applied in total syntheses of (+)-14,15-dihydronorsecurinine (8), (-)-norsecurinine (6), and phyllanthine (2). The B-ring and C7 absolute stereochemistry of these biologically active alkaloids originated from trans-4-hydroxy-L-proline (10), which was converted to ketonitrile 13 via a high-yielding eight-step sequence. Treatment of this ketonitrile with SmI2 afforded the 6-azabicyclo-[3.2.1]octane B/C-ring system 14, which is a key advanced intermediate for all three synthetic targets. Annulation of the A-ring of (-)-norsecurinine (6) with the required C2 configuration via an N-acyliminium ion alkylation was accomplished using radical-based amide oxidation methodology developed in these laboratories as a key step, providing tricycle 33. Annulation of the D-ring onto α-hydroxyketone 33 with the Bestmann ylide 45 at 12 kbar gave (+)-14,15-dihydronorsecurinine (8). In the securinine series, the D-ring was incorporated using an intramolecular Wadsworth-Horner-Emmons olefination of phenylselenylated α-hydroxyketone 47. The C14,15 unsaturation was installed late in the synthesis by an oxidative elimination of the selenoxide derived from tetracyclic butenolide 50 to give (-)-norsecurinine (6). The A-ring of phyllanthine (2) was formed from hydroxyketone 14 using a stereoselective Yb(OTf)3-promoted hetero Diels-Alder reaction of the derived imine 34 with Danishefsky's diene, affording adduct 35. Conjugate reduction and stereoselective equatorial ketone reduction of vinylogous amide 35 provided tricyclicintermediate 36, which could then be elaborated in a few steps to stable hydroxyenone 53 via α-selenophenylenone intermediate 52. The D-ring was then constructed, again using an intramolecular Wadsworth-Horner-Emmons olefination reaction to give phyllanthine (2).