499982-30-8

Upstream product

• 117747-64-5 2-Amino-1-((S)-2,2-dimethyl-4-vinyl-oxazolidin-3-yl)-ethanone 
• 128134-29-2 2-((R)-Benzyloxycarbonylamino-methoxycarbonyl-methyl)-cyclopropanecarboxylic acid ethyl ester 
• 117747-67-8 (1R,2S)-2-((R)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 167937-05-5 (1S,2S)-2-((S)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 129569-91-1 (1S,2S)-2-((R)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 117857-90-6 (1R,2R)-2-((S)-1-tert-Butoxycarbonylamino-2-hydroxy-ethyl)-cyclopropanecarboxylic acid ethyl ester 
• 117747-67-8 (1R,2R)-2-((S)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 117747-67-8 (1R,2R)-2-((R)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 117747-69-0 (1S,5S,6R)-5-(N-(tert-Butoxycarbonyl)amino)-3-oxabicyclo<4.1.0>heptan-2-one 
• 117747-70-3 (1S,2R)-2-((S)-1-tert-Butoxycarbonylamino-2-hydroxy-ethyl)-cyclopropanecarboxylic acid methyl ester 
• 167937-06-6 N-Boc-(2S,3R,4S)-3,4-methanoglutamic acid 
• 1499-55-4 L-glutamic acid 5-methyl ester 
• 117747-67-8 (1S,2R)-2-((R)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 
• 117747-67-8 (1R,2S)-2-((S)-tert-Butoxycarbonylamino-carboxy-methyl)-cyclopropanecarboxylic acid 

Downstream Products

• 128134-30-5 (R)-4-(2-Carboxy-cyclopropyl)-5-oxo-oxazolidine-3-carboxylic acid benzyl ester 
• 128134-31-6 (R)-4-[(R)-2-((R)-2-Hydroxy-1-phenyl-ethylcarbamoyl)-cyclopropyl]-5-oxo-oxazolidine-3-carboxylic acid benzyl ester 
• 128134-31-6 (R)-4-[(S)-2-((R)-2-Hydroxy-1-phenyl-ethylcarbamoyl)-cyclopropyl]-5-oxo-oxazolidine-3-carboxylic acid benzyl ester 

Relevant academic research and scientific papers

Enantio- and diastereocontrolled conversion of chiral epoxides to trans-cyclopropane carboxylates: Application to the synthesis of cascarillic acid, grenadamide and l-(-)-CCG-II

An efficient high yielding improved method for the enantio- and diastereoselective cyclopropanation of chiral epoxides using triethylphosphonoacetate and base (Wadsworth-Emmons cyclopropanation) is reported. The utility of this protocol is illustrated by concise and practical synthesis of cascarillic acid, grenadamide and L-(-)-CCG-II, a cyclopropane containing natural products.

Novel stereocontrolled approach to conformationally constrained analogues of L-glutamic acid and L-proline via stereoselective cyclopropanation of 3,4-didehydro-L-pyroglutamic ABO ester

A new stereocontrolled approach to l-(carboxycyclopropyl)glycines (l-CCGs) and 3,4-methano-l-prolines, conformationally constrained analogues of l-glutamic acid and l-proline, respectively, was developed using a 3,4-didehydro-l- pyroglutamate derivative as a common chiral template. The unsaturated l-pyroglutamate derivative employed in this work is a novel chiral synthon in which the carboxyl functionality is protected as a 2,7,8-trioxabicyclo[3.2.1] octyl group (ABO ester). Stereospecific cyclopropanation of the olefin using diazomethane followed by appropriate functional group interconversion gave l-CCG-III and trans-3,4-methano-l-proline with complete stereocontrol. Synthesis of other diastereomers of l-CCG and cis-3,4-methano-l-proline was accomplished by alteration of the 3,4-methanoglutamic acid framework via carboxycyclopropanation of the olefin with sulfur ylide and subsequent Barton decarboxylation reaction of the original γ-carboxyl group included in the pyroglutamate skeleton.

Reactivity of (Bicyclo[5.1.0]octadienyl)iron(1+) Cations: Application to the Synthesis of cis-2-(2′-Carboxycyclopropyl)glycines

The addition of carbon and heteroatom nucleophiles to (bicyclo[5.1.0]octadienyl)Fe(CO)2L+ cations 5 or 8 (L = CO, PPh3) generally proceeds via attack at the dienyl terminus on the face of the ligand opposite to iron to generate 6-substituted (bicyclo[5.1.0]octa-2,4-diene)iron complexes (11 or 13). In certain cases, these products are unstable with respect to elimination of a proton and the nucleophilic substituent to afford (cyclooctatetraene)Fe(CO)2L (4 or 7). Decomplexation of 13f, arising from addition of phthalimide to 8, gave N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (19). Oxidative cleavage of 19 (RuCl3/NaIO4) followed by esterification gave the cyclopropane diester 22, which upon hydrolysis gave cis-2-(2′ -carboxycyclopropyl)glycine (CCG-III, 18) (eight steps from 4, 43% overall yield). This methodology was also utilized for preparation of stereospecifically deuterated CCG-III (d-18) and optically enriched (-)-18. Deprotonation of 22 resulted in cyclopropane ring opening to afford the benzoindolizidine (23).

Synthesis and reactions of a novel 3,4-didehydropyroglutamate derivative

Some reactions such as catalytic hydrogenation, Diels-Alder reaction, cyclopropanation, dihydroxylation, and Michael addition of a novel 3,4-didehydropyroglutamate derivative, in which the carboxylic group is protected as an ABO ester, are examined and found to take place in a stereospecific manner giving 3- and/or 4-substituted pyroglutamate derivatives without loss of enantiomeric purity at the α-position.

Enantioselective synthesis of L-CCG-I

Introduction of natural menthol as the chiral auxiliary in a γ-Br-α,β-unsaturated ester leads to enantioselective generation of three chiral centers in a single step on reaction with a glycine anion equivalent to provide L-CCG-I in 94% ee.

Synthesis of cyclopropanes via organoiron methodology: Stereoselective preparation of cis-2-(2′-carboxycyclopropyl)glycine

A stereoselective route to cis-2-(2′-carboxycyclopropyl)glycine has been developed. exo-Nucleophilic addition to the (bicyclo[5.1.0]octadienyl)iron(1+) cation establishes the relative stereochemistry at the cyclopropane ring and the α-stereocenter. Subsequent removal of the metal and cleavage of the cyclic diene gave the protected target 10, which upon hydrolysis gave 1.

An efficient and stereoselective synthesis of (2S,1′S,2′S)-2-(carboxycyclopropyl) glycine (LCCG-I): Conformationally constrained L-glutamate analogues

Conformationally restricted metabotropic glutamate receptor agonist (2S,1′S,2′S)-2-(Carboxycyclopropyl) glycine (LCCG-I) 1 have been efficiently synthesized in a stereoselective manner. A convenient five step synthesis of 1 from readily available (-)-dime

Novel enantioselective synthesis of trans-α-(2-carboxycyclo-prop-1- yl)glycines: Conformationally constrained L-glutamate analogues

D- and L-α-(2-carboxycycloprop-1-yl)glycines were synthesized from trans-1,3-di(2-furyl)propenone. Conversion of the double bond to a cyclopropane is followed by the formation of an oxime ether. Enantioselective reduction of the oxime ether, separation of diastereomers and oxidation of the furane rings gave enantiomerically pure D- and L-CCG I and CCG II. The structure of oxime 7b was determined by X-ray crystal structure analysis. The key step is the oxazaborolidine catalyzed enantioselective conversion of oxime ethers to amines.

Facile synthesis of (2S,1'S,2'S)-2-(carboxycyclopropyl)glycine an isotype-selective agonist of metabotropic glutamate receptors

(2S,1'S,2'S)-2-(Carboxycyclopropyl)glycine (L-CCG-I) was synthesized in 12 steps and 14% overall yield by using Sharpless's asymmetric dihydroxylation reaction and stereochemically controlled cyclopropanation as key steps.