88002-15-7

Upstream product

• 25726-04-9 phenylglyoxylyl chloride 
• 65253-04-5 (-)-8-phenylmenthol 
• 71804-27-8 (1R,2S,5R)-(+)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl chloroacetate 
• 611-73-4 Benzoylformic acid 

Downstream Products

• 98510-13-5 (1R,5R,7S)-3,3-Dimethyl-7-phenyl-2,4,6-trioxa-bicyclo[3.2.0]heptane-7-carboxylic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 98510-13-5 (1S,5S,7R)-3,3-Dimethyl-7-phenyl-2,4,6-trioxa-bicyclo[3.2.0]heptane-7-carboxylic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 97291-79-7 <(1R,2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)cyclohexyl>-3,3,4,4-tetraethoxy-2-phenyl-2-oxetancarboxylat 
• 88292-45-9 (1'R,2'S,5'R)-2'-(1-methyl-1-phenylethyl)-5'-methylcyclohexyl (R)-2-hydroxy-2-phenylpropanoate 
• 142798-17-2 (R)-2-Hydroxy-2-phenyl-butyric acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 88002-09-9 (R)-2-Hydroxy-2-phenyl-succinic acid 4-ethyl ester 1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl] ester 
• 88002-27-1 (S)-2-Hydroxy-2-phenyl-succinic acid 4-ethyl ester 1-[(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl] ester 
• 88080-34-6 (S)-3,3-Diethoxy-2-phenyl-oxetane-2-carboxylic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 88002-02-2 (R)-3,3-Diethoxy-2-phenyl-oxetane-2-carboxylic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 88002-09-9 4-Ethyl-1-<(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl>-2-hydroxy-2-phenylsuccinat 
• 88002-02-2 <(1R,2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)cyclohexyl>-3,3-diethoxy-2-phenyl-2-oxetancarboxylat 
• 153993-87-4 (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl-(S)-α-hydroxy-α-<4-(2-hydroxyethyl)phenyl>benzeneacetate 
• 153993-90-9 (S)-α-hydroxy-α-<4-(2-fluoroethyl)phenyl>benzeneacetic acid 
• 97371-54-5 (-)-(2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)cyclohexanon 

Relevant academic research and scientific papers

Selective Formation of Functionalized α-Quaternary Malononitriles toward 5,5-Disubstituted Pyrrolopyrimidinones

A modular, selective approach to complex α-tertiary substituted malononitriles is reported. The method takes advantage of β-ester-substituted α,α-dinitrile alkenes as highly reactive, chemoselective electrophiles for 1,4-additions with organometallic nucleophiles to produce functionally and sterically dense all-carbon quaternary centers. In the presence of a chiral ester auxiliary bearing an aromatic ring, the 1,4-addition occurs with good to excellent selectivity due to favorable cation-π interactions. The highly functionalized malononitriles represent versatile building blocks and can be applied toward efficient, highly selective syntheses of 5,5-disubstituted pyrrolopyrimidinones.

Dimethylzinc-mediated addition of alkenylzirconocenes to α-keto and α-imino esters

(Matrix presented) Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.

Diatereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of α-Hydroxy and α-Alkoxy Esters

A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)-menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)-10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding α-keto esters 1 by way of the tosylhydrazones 2.Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity.A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results.The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration.Possible mechanisms are discussed.

Asymmetric Reactions of 8-Phenylmenthyl Pyruvate with Allyltrimethylsilane, Silyl Enol Ethers and Ketene Silyl Acetals

By mediation of TiCl4, allylsilane, silyl enol ethers and ketene silyl acetals attacked (-)-phenylmenthyl pyruvate and (-)-phenylmenthyl phenylglyoxylate at their si-faces.The reactions are hypothesised to proceed with rigid cyclic transition states: anti aldol adducts 16 and 17a were favourably obtained from E-ketene silyl acetals 6 and 7 having E-configuration, whereas syn aldol adducts 18b-21b were predominantly obtained from Z-ketene silyl acetal 18 and Z-silyl enol ethers 19-21.

Asymmetric syntheses with a new optically active perhydronaphthalene based chiral auxiliary

(1R,4aS,8S,8aS)-8-(5'-Methoxy-2'-methylphenyl)-8-methyldecahydro-1-nap hthalenol 3a is a highly efficient chiral auxiliary in the Diels-Alder addition of its acrylate ester 5 and in the DIBAL-H and Grignard reactions of its phenylglyoxylate ester 7.

Asymmetric synthesis of benzilic acid analogues using 8-phenylmenthol as a chiral auxiliary

Our program on the synthesis of 18F-labeled muscarinic receptor ligands required the preparation of chiral fluoroalkyl benzilic acids. An enantioselective synthesis of substituted benzilic acids was achieved using 8-phenylmenthol as the chiral auxiliary. Grignard addition to the si face of 8-phenylmenthyl benzoylformate 7 proceeded with high selectivity. The results of the chiral induction support assignments of the chirality of benzilic acids previously resolved by crystallization. The method was used to synthesize (R)-quinuclidinyl-(R)-4-iodo)benzilate, which proved identical to an authentic sample. In addition, the method allows the preparation of (R)- and (S)-fluoroethyl benzilic acids in a stereoselective manner.

DIASTEREOSELECTIVE REDUCTION OF AN α-KETO-ESTER DERIVED FROM (-)-8-PHENYLMENTHOL: A 4-step synthesis of R-Halostachine analogue

An efficient (80percent total yield) 4-step synthesis of 94percent e.e.R-(-)-Halostachine analogue is described.The method offers the possibility to introduce various substituents onto the aromatic ring and various alkyl groups on the amine.A one-step and high yield (ca.100percent) conversion of esters into amides is presented.

Chiral Induction in Photochemical Reactions, II - Regio- and Diastereoselectivity in the Oxetane Formation of Chiral Phenylglyoxylates with Electron Rich Olefins

In the photochemical oxetane formation of chiral phenylglyoxylates with 3 high diastereoselectivities and lower regioselectivities are achieved with 1a and 1d.The lower regio- and diastereoselectivities observed with 1c, 1e, and 1g can be rationalized by the influence of the chiral alcohol on the conformation of the keto ester and on the different steric hindrances of the cis (face-position) or trans (edge-position) diradicals 5 or 7.In agreement with this model the differences of activation parameters obtained for the regio- and diastereoselectivities of 5b and 7b are discussed.By variation of the starting olefins we observed an increase of the diastereoselectivity of oxetane formation in the sequence 8 ca. 7 5 4, caused by increasing control of the cis-diradical (face-position).