124931-81-3

Basic information

• Product Name: (R_a)-phenylacetic acid 2'-hydroxy[1,1']binaphthalenyl-2-ester
• CAS NO: 124931-81-3
• Molecular Weight: 404.465
• Mol File: 124931-81-3.mol
• Article Data: 3

Chemical Properties

• CAS DataBase Reference: (R_a)-phenylacetic acid 2'-hydroxy[1,1']binaphthalenyl-2-ester(CAS DataBase Reference)
• NIST Chemistry Reference: (R_a)-phenylacetic acid 2'-hydroxy[1,1']binaphthalenyl-2-ester(124931-81-3)
• EPA Substance Registry System: (R_a)-phenylacetic acid 2'-hydroxy[1,1']binaphthalenyl-2-ester(124931-81-3)

Safety Data

• Hazardous Substances Data: 124931-81-3(Hazardous Substances Data)

Upstream product

• 103-82-2 phenylacetic acid 
• 1555-80-2 phenylacetic anhydride 
• 602-09-5 1,1'-bi-2-naphthol 
• 18531-94-7 (R)-1,1'-Bi-2-naphthol 
• 103-80-0 phenylacetyl chloride 

Downstream Products

• 13491-13-9 (R)-2-isopropyl-2-phenylacetic acid 
• 474317-49-2 (-)-(2R,3R)-2-phenyl-3-(4-trifluoromethylphenyl)-1,4-butanediol 
• 474317-48-1 (-)-(2R,3R)-2-(4-methoxyphenyl)-3-phenyl-1,4-butanediol 

Relevant articles and documents

Isothiourea-Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols

An operationally simple isothiourea-catalysed acylative kinetic resolution of unprotected 1,1′-biaryl-2,2′-diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high s values; ii) the use of an α,α-disubstituted mixed anhydride (2,2-diphenylacetic pivalic anhydride) was critical to minimize diacylation and give high selectivity; iii) the presence of substituents in the 3,3′-positions of the diol hindered effective acylation. This final observation was exploited for the highly regioselective acylative kinetic resolution of unsymmetrical biaryl diol substrates bearing a single 3-substituent. Based on the key observations identified, acylation transition state models have been proposed to explain the atropselectivity of this kinetic resolution.

1,1′-binaphthalene-2,2′-diol as a chiral auxiliary. Diastereoselective alkylation of binaphthyl esters, complex-induced proximity effects in enolate formation, and one-step synthesis of an optically active β-substituted ketone

Diastereoselective alkylation of enolates derived from (S)-naphthyl phenylacetate 1 with LDA in THF gave the S,S-isomer as a major product. The diastereoselectivity increased as the bulkiness of the alkylating agent was increased. The low diastereomeric excess (～70%) of methylation was markedly raised to 92% by the use of n-BuLi as a base due to the complex-induced proximity effect (CIPE) in enolate formation. This highly diastereoselective methylation was used to synthesize the clinically important anti-inflammatory drugs (S)-naproxen (60) and (S)-suprofen (68). The stereochemistry of ketene trimethylsilyl acetals generated from several phenylacetates was investigated to understand the origin of the diastereoselectivity in this alkylation. Methyl phenylacetate (46) predominantly gave a (Z)-enolate by kinetic deprotonation, while the (E)-enolate was predominantly obtained from phenyl phenylacetate (47). An optically active ketone (88) was synthesized from binaphthyl ester 84 by a one-pot procedure involving the 1,4-addition, followed by the 1,2-addition, of organometallics. The CIPE again played a crucial role in the high enantiomeric excess in this case.