30990-90-0

Upstream product

• 100-39-0 benzyl bromide 
• 74807-91-3 (2S)-2-Methoxymethyl-N-(1-methyl-3-trimethylsilyl-2-propynyl)-1-pyrrolidinemethanimine 
• 126402-81-1 isopropyl 2-[(E)-1-phenylmethylideneamino]propanoate 
• 123618-23-5 ethyl (2S)-2-acetylamino-2-methyl-3-phenylpropanoate 
• 245338-82-3 N-4-fluorobenzylidene-DL-Ala isopropyl ester 
• 245338-81-2 isopropyl 2-[(E)-1-(4-chlorophenyl)methylideneamino]propanoate 
• 946414-69-3 (3S,6S)-3-benzyl-3-methyl-6-isopropyl-piperazine-2,5-dione 
• 1063964-53-3 (3S,6R)-3-benzyl-6-(methoxymethyl)-3,6-dimethyl-5-phenyl-3H-1,4-oxazin-2(6H)-one 
• 1266680-98-1 (3S,5aR,6aS,7aS)-3-benzyl-5,5a,6,6a,7,7a-hexahydro-3,6,6,7a-tetramethylbicyclo[4.1.0]hept-1⁽⁶⁾eno[3,4-b][1,4]oxazin-2(3H)-one 
• 100-44-7 benzyl chloride 
• 946414-68-2 (3R,6S)-3-benzyl-3-methyl-6-isopropyl-piperazine-2,5-dione 
• 1063964-44-2 (3R,6R)-3-benzyl-6-(methoxymethyl)-3,6-dimethyl-5-phenyl-3H-1,4-oxazin-2(6H)-one 
• 143238-85-1 benzo[d][1,3]dioxol-5-ylmethyl diethyl phosphate 
• 346578-00-5 (2S,4R)-4-Benzyl-2-biphenyl-4-yl-4-methyl-5-oxo-oxazolidine-3-carboxylic acid isobutyl ester 

Downstream Products

• 28385-45-7 L-α-methylphenylalanine methyl ester 

Relevant academic research and scientific papers

Benzylic phosphates as electrophiles in the palladium-catalyzed asymmetric benzylation of azlactones

Palladium-catalyzed asymmetric benzylation has been demonstrated with azlactones as prochiral nucleophiles in the presence of chiral bisphosphine ligands. Benzylic electrophiles are utilized under two sets of reaction conditions to construct a new tetrasubstituted stereocenter. Electron density of the phenyl ring dictates the reaction conditions, including the leaving group. The reported methodology represents a novel asymmetric carbon-carbon bond formation in an amino acid precursor.

Asymmetric synthesis of α-methyl-α-amino acids via diastereoselective alkylation of (1s)-(+)-3-carene derived tricyclic iminolactone

A novel carene-based alanine-equivalent tricyclic iminolactone 16 has been synthesized via stereoselective dihydroxylation of the double bond, IBX oxidation of the secondary alcohol, esterification of the tertiary alcohol, deprotection of the resulting ester, and subsequent cyclization from commercially available (1S)-(+)-3-carene in 79% overall yield. The iminolactone 16 demonstrated high reactivity toward alkylation with a wide range of electrophiles at room temperature under phasetransfer catalysis conditions. The alkylated products were produced with excellent diastereoselectivities (>98% de) in good isolated yields (86-94%). High yields (83-91%) of optically pure (S)-R-methyl-R-substituted-R-amino acids were obtained by basic hydrolysis of the dialkylated iminolactones with the recovery of the chiral auxiliary 15 (78-87%).

Asymmetric synthesis of α-amino acids: Preparation and alkylation of monocyclic iminolactones derived from α-methyl trans-cinnamaldehyde

(Chemical Equation Presented) Two novel chiral monocyclic iminolactones 14a and 14b have been prepared. The chiral auxiliary 12 was obtained from α-methyl-trans-cinnamaldehyde through reduction, methylation, Sharpless asymmetric dihydroxylation, and oxidation in 87% overall yield. Esterification of compound 12 with the respective protected amino acids followed by deprotection and cyclization provided the corresponding iminolactones, each in 82% overall yield. Alkylation of the iminolactone 14a afforded the α-methyl-α,α-disubstituted products 15 and 16 in good yields (78-99%) and excellent diastereoselectivity (de >98%). Alkylations of the iminolactone 14b furnished the α-benzyl-α,α-disubstituted products 15a, 16b, 17, and 18 in good yields (51-86%) but moderate diastereoselectivities (43-56%). When HMPA or DMPU was used as a cosolvent, the rate of alkylation of the iminolactone 14b was accelerated with improved yields (56-99%) and diastereoselectivities (50-83%). Hydrolysis of the dialkylated iminolactones yielded the α,α-disubstituted α-amino acids in good yields (80-98%) and high enantiomeric excesses (98-99%) with good recovery of compound 12 (83-92%).

Enantioselective [1,2]-Stevens rearrangement using sugar-derived alkoxides as chiral promoters

The first example of enantioselective base-induced [1,2]-Stevens rearrangement was achieved by using the newly developed D-glucose-derived lithium alkoxide as a chiral promoter. This rearrangement provides an α-amino ketone having a pseudoquaternary chira

Diastereoselective synthesis of quaternary α-amino acids from diketopiperazine templates

Sequential enolate alkylations of (S)-N(1)-methyl-5-methoxy-6-isopropyl-3, 6-dihydropyrazin-2-one and (S)-N(1)-p-methoxybenzyl-5-methoxy-6-isopropyl-3,6- dihydropyrazin-2-one proceed with excellent levels of diastereoselectivity (>90% de) affording quaternary α-amino acids in high enantiomeric excess (>98% ee) after deprotection and hydrolysis. This journal is The Royal Society of Chemistry.

A PROCESS FOR RESOLVING RACEMIC MIXTURES AND A DIASTEREOISOMERIC COMPLEX OF A RESOLVING AGENT AND AN ENANTIOMER OF INTEREST

A process for resolving a compound in racemic form comprising the following steps is described: a) reacting a compound in racemic form with a resolving agent, b) forming a diastereoisomeric complex of the resolving agent and an enantiomer of interest, c} separating the enantiomer of interest from the obtained diastereoisomer, wherein such a process is characterized in that said resolving agent is a compound of Formula (I). A diastereoisomeric complex between the resolving agent of Formula (I) and the enantiomer of interest is also described. The process according to the invention allows acid and basic racemic mixtures to be separated.

Crystallization-induced asymmetric transformations and self-regeneration of stereocenters (SROSC): Enantiospecific synthesis of α-benzylalanine and hydantoin BIRT-377

N-Isobutoxycarbonyl protected L-alanine was condensed with 4-phenylbenzaldehyde in a crystallization-controlled process to give the corresponding cis-oxazolidinone derivative as the sole product in high yield; this underwent enolization and benzylation wi

Chiral environment specifically induced by metal ion: Asymmetric α- alkylation of α-amino esters using pyridoxal derivatives having a chiral ionophore function

Stereoselective alkylation of aldimines, prepared from α-amino esters and pyridoxal models having an ionophoric side-chain composed of a chiral glycerol structure, proceeded in the presence of Li+ or Na+ to afford α,α-dialkyl amino esters after acidic hydrolysis. Both the structure of the side chain and the metal ion were found to be in relation with the stereoselectivity, affording the highest stereoselectivity when the side- chain having a 2-naphthylmethoxy group and a methoxy group at the respective 3'- and 2'-positions was employed in the presence of Na+.

Asymmetric alkylation catalyzed by chiral alkali metal alkoxides of TADDOL. Synthesis of α-methyl amino acids

It is shown that sodium alkoxides formed from (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-bis(diphenylmethanol) ((R,R)-TADDOL) and some of its derivatives can be used as chiral catalysts for enantioselective alkylation of Schiff's bases derived from alanine with reactive alkyl halides. Acid hydrolysis of the reaction products affords (R)-α-methytphenyl-alanine, (R)-α-allylalanine, and (R)-α-methylnaphthylalanine in 61-93% yields and with ee 69-94%. When (S,S)-TADDOL is used, the (3)-amino acid is formed. A mechanism explaining the observed features of the reaction is proposed.

Enantiomerically enriched (R)- and (S)-α-methylphenylalanine via asymmetric PTC C-alkylation catalysed by NOBIN

Enantiopure 2-hydroxy-2'-amino-1,1'-binaphthyl (NOBIN) is shown to catalyse C-alkylation of aldimine Schiff's bases of alanine ester under phase-transfer catalysis conditions (solid NaOH or NaH, toluene, ambient temperature, 10% NOBIN). Using (R)-NOBIN, t