69684-81-7

Upstream product

• 102371-35-7 (1,2-bis-ethoxycarbonyl-4-isopropenyl-pyrrolidin-3-yl)-malonic acid diethyl ester 
• 87682-50-6 (+/-)-4c-isopropenyl-3t-methoxycarbonylmethyl-pyrrolidine-1,2r-dicarboxylic acid-1-ethyl ester-2-methyl ester 
• 132286-59-0 Benzoic acid (2S,3S,4R)-1-benzoyl-4-isopropenyl-3-methoxycarbonylmethyl-pyrrolidin-2-ylmethyl ester 
• 108072-03-3 (2R,3S,4R)-1-Benzyl-4-isopropenyl-3-methoxycarbonylmethyl-pyrrolidine-2-carboxylic acid methyl ester 
• 77632-78-1 (-)-menthyl(Z)-4,4-diethoxycarbonyl-4--2-butenoate 
• 92180-18-2 (-)-menthyl(Z)-4,4-diethoxycarbonyl-4-trifluoroacetamido-2-butenoate 
• 92180-18-2 (-)-menthyl(E)-4,4-diethoxycarbonyl-4-trifluoroacetamido-2-butenoate 
• 77632-78-1 (-)-menthyl(E)-4,4-diethoxycarbonyl-4--2-butenoate 
• 92180-27-3 menthyl trans-(2,2-diethoxycarbonyl-4-isopropenyl-1-trifluoroacetylpyrrolidin-3-yl)acetate 
• 103871-64-3 N-t-butoxycarbonyl-3α-methoxycarbonylmethyl-4β-acetyl-α-proline-ethyl-ester 
• 88171-39-5 (3aS,4aS,5R,6S,7R,8aR)-5-Acetyl-6-(2-benzyloxy-ethyl)-8a-methyl-octahydro-furo[2,3-d]pyrrolo[2,1-b]thiazole-7-carboxylic acid ethyl ester 
• 88171-41-9 N-t-butoxycarbonyl-3α-(2-benzyloxyethyl)-4β-acetyl-α-proline-ethyl-ester 
• 132286-62-5 ((2R,3R,4S)-1-Benzoyl-2-hydroxymethyl-4-isopropenyl-pyrrolidin-3-yl)-acetic acid methyl ester 
• 101572-13-8 3-acetoxy-4-(β-dimethylamino-isopropyl)-pyrrolidine-1,2-dicarboxylic acid diethyl ester 

Downstream Products

• 487-79-6 (-)-kainic acid 

Relevant academic research and scientific papers

Synthesis of (±)-β-Allokainic Acid

The total synthesis of kainoid alkaloid, (+/–)-β-allokainic acid is reported. The key step is a vinylogous Cloke–Wilson rearrangement followed by Lewis acid and transition metal induced transformations to prepare a highly functionalized pyrrolidine suitable for conversion to the target molecule.

Substrate stereocontrol in the intramolecular organocatalyzed tsuji-trost reaction: Enantioselective synthesis of allokainates

Organocatalyzed Tsuji-Trost cyclization of 3b proceeds with asymmetric induction and allows for stereoselective synthesis of (+)-allokainic acid. The stereochemical outcome of the cyclization was predicted by calculations.

Total synthesis of (±)-kainic acid: A photochemical C-H carbamoylation approach

A novel photochemical C-H carbamoylation of an octahydroisoindole derivative with PhNCO has allowed the authors to provide a unique access to a highly functionalized proline motif from which total synthesis of (±)-kainic acid, a bioactive marine alkaloid, has been accomplished.

Di- and trisubstituted γ-lactams via Rh(II)-carbenoid reaction of N -Cα-branched, N -Bis(trimethylsilyl)methyl α-diazoamides. Synthesis of (±)-α-allokainic acid

Acyclic N-Cα-branched, N-bis(trimethylsilyl)methyl (N-BTMSM) diazoamides undergo regio-, chemo-, and diastereoselective Rh(II)-carbenoid C-H insertion to give 4,5-disubstituted and 3,4,5-trisubstituted γ-lactams. The conformational influence of

Ruthenium-catalyzed cycloisomerizations of diynols

A wide variety of diynols containing tertiary, secondary, and primary propargylic alcohols undergo a cycloisomerization reaction to form dienones and dienals in the presence of a catalytic amount of [CpRu(CH3CN) 3]PF6. The

Stereocontrolled syntheses of kainoid amino acids from 7-azabicyclo[2.2.1] heptadienes using tandem radical addition-homoallylic radical rearrangement

N-Boc syn-7-(2-hydroxyethyl)-4-(alkyl or aryl)sulfonyl-2-azabicyclo[2.2.1] hept-5-enes serve as precursors in syntheses of the neuroexcitants 3-(carboxymethyl)pyrrolidine-2,4-dicarboxylic acid 43, α-kainic acid 12, α-isokainic acid 14, and α-dihydroalloka

Total synthesis of (+/-)-kainic Acid with an aza-[2,3]-Wittig sigmatropic rearrangement as the key stereochemical determining step.

A flexible route to the kainoid skeleton is exemplified by the synthesis of (+/-)-kainic acid from 3-butyn-1-ol. The route relies on the aza-[2,3]-Wittig sigmatropic rearrangement to efficiently install the relative stereochemistry between C2-C3. The C4 s

Synthesis of (±)-kainic acid by dearomatising cyclisation of a lithiated N-benzyl p-anisamide

N-Benzyl p-anisamide 6, on lithiation with Bu(t)Li in the presence of HMPA, undergoes a stereoselective anionic cyclisation with loss of aromaticity to give a bicyclic enone which may be converted in nine steps to (±)-kainic acid.

Stereoselective synthesis of (±)-α-kainic acid using free radical key reactions

Thiol-mediated free radical isomerization of a deliberately substituted but-3-enyl isocyanide 12a, and n-Bu3SnH/AIBN-mediated free radical cyclization of a deliberately substituted but-3-enyl isothiocyanate 22, afforded, respectively, the (ethylthio)pyrroline 13a and the thiopyroglutamates 5 and 23. Reduction, protection, and deprotection of these heterocyclic compounds afforded proline derivatives 6 and 25 which contain all the structural elements of α-kainic acid (1) except the C-2 acetic acid moiety. These intermediates were stereospecifically converted into (±)-α-kainic acid using a new method of temporary sulfur connection. Accordingly, CH2CO2Me is linked to the chiral isopropenyl anchor and then intramolecularly connected to the pyrrolidine ring and eventually disconnected from its anchor by a sequential reductive double elimination process in which the isopropenyl double bond is restored.

A Concise, Stereocontrolled Thiazolium Ylide Approach to Kainic Acid

Racemic α-kainic acid (1) has been prepared from (1SR,2SR,5RS)-ethyl (N-(benzyloxycarbonyl)-3-aza-6-oxobicyclooctane-2-carboxylate (11) in ca. 16percent overall yield via a concise six-step synthetic sequence.Compound 11 is prepared on a large scale in 50percent yield via the cycloaddition of thiazolium ylide 9 and 2-cyclopentenone, which provides the requisite 2,3-trans, 3,4-cis stereochemical array about the trisubstituted pyrrolidine nucleus in 1.Chemoselective addition of the one-to-one adduct of MeLi and TiCl4 to the ketone functionality in 11 followed by dehydration, oxidative ring opening, and nonbasis methylenation of the stereochemically labile C4 acetate moiety with CH2I2-Zn-TiCl4 affords the fully protected penultimate intermediate 17 which is exhaustively hydrolyzed to provide 1.This represents a highly efficient and stereocontrolled preparation of (+/-)-α-kainic acid.