104870-75-9

Upstream product

• 67-56-1 methanol 
• 126378-69-6 (R)-2-Isobutyl-4-oxo-5-triisopropylsilanyl-3,4-dihydro-2H-pyridine-1-carboxylic acid (1S,2R,5S)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 89-82-7 pulegone 
• 104870-79-3 (2R,5R)-2-(1-methyl-1-phenylethyl)-5-methylcyclohexanone 
• 849113-77-5 (+)-(1S,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl glyoxylate 
• 849113-76-4 (+)-(1S,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl acrylate 
• 1427281-86-4 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1S)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 
• 1427281-84-2 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1R)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 
• 205057-17-6 (5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexanone 
• 100-58-3 phenylmagnesium bromide 
• 5949-05-3 (S)-Citronellal 
• 98-09-9 benzenesulfonyl chloride 
• 104870-80-6 (1R,2R,5R)-2-(1-methyl-1-phenylethyl)-5-methylcyclohexanol 
• 65253-04-5 (-)-8-phenylmenthol 

Downstream Products

• 71804-27-8 (1R,2S,5R)-(+)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl chloroacetate 
• 75863-05-7 Malonic acid bis-[(2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl] ester 
• 97371-54-5 (-)-(2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)cyclohexanon 
• 849113-76-4 (+)-(1S,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl acrylate 
• 322640-03-9 (1S,2S,5R)-5-methyl-2-[1-methyl-(1-phenyl)ethyl]cyclohexyl acetate 
• 849113-77-5 (+)-(1S,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl glyoxylate 
• 849113-74-2 (1R,3R,4S)-2-Benzyl-2-aza-bicyclo[2.2.1]hept-5-ene-3-carboxylic acid (1S,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 167304-67-8 2-Diazo-3-oxo-6-phenyl-hexanoic acid (1S,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 1427281-86-4 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1S)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 
• 1427281-84-2 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1R)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 
• 1427281-90-0 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1S)-1-phenylethyl]piperidine-2-carboxylate 
• 1427281-88-6 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1R)-1-phenylethyl]piperidine-2-carboxylate 
• 129180-87-6 (-)-8-phenylmenthol phenylcarbamate 
• 129180-87-6 Phenyl-carbamic acid (1S,2R,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 

Relevant academic research and scientific papers

A short, efficient synthesis of the chiral auxiliary (+)-8- phenylneomenthol

(+)-8-Phenylneomenthol 2, the structure of which was confirmed by X-ray analysis of its 3,5-dinitrobenzoate, was efficiently prepared from commercially available (-)-8-phenylmenthol 3 by oxidation with the Sarett reagent, followed by L-Selectride reduction of the (+)-8-phenylmenthone 6 thus formed. (C) 2000 Elsevier Science Ltd.

Diastereoselective photocycloaddition reactions of 2-naphthalenecarboxylates and 2,3-naphthalenedicarboxylates with furans governed by chiral auxiliaries and hydrogen bonding interactions

By using chiral auxiliaries and hydrogen bonding interactions, we have developed diastereoselective photocycloaddition of 2-naphthalenecarboxylates and 2,3-naphthalenedicarboxylates with furan derivatives. In photoreactions of (?)-menthyl 2-naphthalenecarboxylate with furan and 3-furanmethanol, respective maximum 48% and 40% diastereomeric excesses (d.e.) are observed. In photoreactions of di-8-phenyl-(?)-menthyl 2,3-naphthalenedicarboxylate with 3-furanmethanol, maximum 67% d.e. is obtained. Use of solvents of low polarity, low temperatures and low furan concentration leads to increased diastereoselectivities. Variable-temperature (VT) NMR and fluorescence quenching studies indicate that hydrogen bonding interactions between the carbonyl oxygen of naphthalenecarboxylic acid esters and the OH group in 3-furanmethanol take place in both the ground and excited states. The results of computational studies show that geometries of C2 symmetric naphthalenedicarboxylate reactants are important in governing the high diastereoselectivity in the photoreactions of 2,3-naphthalenedicarboxylates.

Synthesis of the Privileged 8-Arylmenthol Class by Radical Arylation of Isopulegol

Hydrogen atom transfer (HAT) circumvents a disfavored Friedel-Crafts reaction in the derivatization of the inexpensive monoterpene isopulegol. A variety of readily prepared aryl and heteroaryl sulfonates undergo a formal hydroarylation to form 8-arylmenthols, privileged scaffolds for asymmetric synthesis, as typified by 8-phenylmenthol. High stereoselectivity is observed in related systems. This use of HAT significantly extends the chiral pool from the inexpensive monoterpene isopulegol.

Asymmetric 1,2-Perfluoroalkyl Migration: Easy Access to Enantioenriched α-Hydroxy-α-perfluoroalkyl Esters

This study has led to the development of a novel, highly efficient, 1,2-perfluoro-alkyl/-aryl migration process in reactions of hydrate of 1-perfluoro-alkyl/-aryl-1,2-diketones with alcohols, which are promoted by a Zn(II)/bisoxazoline and form α-perfluoro-alkyl/-aryl-substituted α-hydroxy esters. With (-)-8-phenylmenthol as the alcohol, the corresponding menthol esters are generated in high yields with excellent levels of diastereoselectivity. The mechanistic studies show that the benzilic ester-type rearrangement reaction takes place via an unusual 1,2-migration of electron-deficient trifluoromethyl group rather than the phenyl group. The overall process serves as a novel, efficient, and simple approach for the synthesis of highly enantioenriched, biologically relevant α-hydroxy-α-perfluoroalkyl carboxylic acid derivatives.

Highly stereoselective cycloadditions of Danishefsky's diene to (-)-8-phenylmenthyl and (+)-8-phenylneomenthyl glyoxylate N-phenylethylimines

Enantiopure 4-oxo-pipecolic acid derivatives were obtained by double asymmetric induction aza-Diels-Alder reactions between chiral glyoxylate N-phenylethylimines and Danishefsky's diene mediated by zinc iodide. The key to success was the use of iminoacetates possessing two chiral auxiliaries, N-(S)- or N-(R)-1-phenylethyl and (-)-8-phenylmenthyl or (+)-8-phenylneomenthyl. Adducts were formed in good yields (78-81%), with complete regioselectivity and high diastereoselectivity (87-96%). The absolute configuration of the adducts formed was unequivocally assigned through NMR, specific optical rotation and X-ray data of appropriated derivatives. These cycloadducts can serve as precursors for bioactive piperidinic azasugars and pipecolic acid derivatives.

Enantioselective synthesis of [(1R,3-exo)-2-benzyl-2-azabicyclo[2.2.1]hept- 5-en-3-yl]methanol via Aza-Diels-Alder reaction

The asymmetric aza-Diels-Alder reaction of the 8-phenylneomenthyl (or 8-phenylisomenthyl) glyoxylate-derived N-benzylimine with cyclopentadiene resulted in the enantioselective synthesis of the corresponding [(1R,3-exo)-2-benzyl-2-azabicyclo[2.2.1]hept-5-

Chiral auxiliaries for asymmetric radical cyclization reactions: application to the enantioselective synthesis of (+)-triptocallol.

[figure: see text] A series of epimeric 8-aryl menthyl derivatives 5a-d and 6a-l, prepared from the same chiral source (R)-pulegone, were employed as chiral auxiliaries in the asymmetric radical cyclization reactions of beta-keto esters mediated by Mn(OAc)3. Chiral precursors 8c and 8d provided the cyclization products 10c and 10d, respectively, as single isomers (dr > 99:1), whereas the cyclization of precursor 9k gave 13k with good stereoselectivity (dr = 24:1). Diastereomer 13e was employed as the key intermediate in the enantioselective synthesis of (+)-triptocallol in 90% ee.

Synthesis and characterization of all stereoisomers of 8-phenylmenthol

New, improved and/or specific syntheses of the diastereoisomers of (-)-8-phenylmenthol are described. The configurations of these products, usable as chiral auxiliaries, were confirmed by X-ray diffractometry of their 3,5-dinitrobenzoates.

Asymmetric Synthesis of 2-Alkyl(Aryl)-2,3-dihydro-4-pyridones by Addition of Grignard Reagents to Chiral 1-Acyl-4-methoxypyridinium Salts

Grignard addition to a chiral 1-acyl-4-methoxypyridinium salt provides synthetically useful 2-alkyl(aryl)-2,3-dihydro-4-pyridones in high diastereomeric excess.