849113-76-4

Upstream product

• 97371-54-5 (-)-(2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)cyclohexanon 
• 104870-75-9 (1S,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)-cyclohexan-1-ol 
• 814-68-6 acryloyl chloride 

Downstream Products

• 1433821-97-6 (+)-8-phenylneomenthyl (1R,4R,5R)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate 
• 1433822-02-6 (t)-8-phenylneomenthyl (1S,4S,5S)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate 
• 1433821-67-0 (+)-8-phenylneomenthyl glyoxylate oxime 
• 1333161-40-2 (+)-(1S,3R,4R)-2-[(1R)-1-phenylethyl]-3-[(1S,2S,5R)-8-phenylneomenthyl-oxycarbonyl]-2-azabicyclo[2.2.1]hept-5-en-2-ammonium trifluoroacetate 
• 1333161-39-9 (+)-(1S,2S,5R)-8-phenylmenthyl (1S,3R,4R)-2-[(1R)-1-phenylethyl]-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate 
• 1333161-38-8 (-)-(1S,2S,5R)-8-phenylmenthyl (1S,3S,4R)-2-[(1R)-1-phenylethyl]-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate 
• 1333161-37-7 (+)-(1S,2S,5R)-8-phenylmenthyl (1R,3R,4S)-2-[(1R)-1-phenylethyl]-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate 
• 1333161-34-4 (+)-(1S,2S,5R)-8-phenylmenthyl (1R,3R,4S)-2-[(1S)-1-phenylethyl]-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate 
• 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 
• 1427281-88-6 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1R)-1-phenylethyl]piperidine-2-carboxylate 
• 1427281-90-0 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1S)-1-phenylethyl]piperidine-2-carboxylate 
• 1427281-84-2 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1R)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 
• 1427281-86-4 (+)-(1S,2S,5R)-8-phenylneomenthyl (2R)-4-oxo-1-[(1S)-1-phenylethyl]-1,2,3,4-tetrahydropyridine-2-carboxylate 

Relevant academic research and scientific papers

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.

The origin of stereoselectivity in cycloaddition reactions promoted by stereoisomers of 8-phenylmenthyl glyoxylate oxime

A structural study of three synthesized stereoisomeric oximes, (-)-8-phenylmenthyl glyoxylate oxime (8-PMGO), (+)-8-phenylneomenthyl glyoxylate oxime (8-PnMGO), and (-)-8-phenylisoneomenthyl glyoxylate oxime (8-PinMGO), was performed by means of variable temperature 1H NMR spectroscopy, X-ray crystallography, and ab initio calculations. It was found that in 8-PMGO a conformation where the phenyl and oxime moieties are stacked is significantly favored, whereas in the other stereoisomers this preference was not so evident. The conformational differences found between the isomers were used to rationalize the outcome of the reaction (simultaneous 1,3-cycloaddition and aza-Diels-Alder reaction) between the referred oximes and cyclopentadiene, in which the stereoselectivity was evaluated and found to be nicely reproduced by a simple conformational analysis. The global results indicate that the stereoselectivity of the studied oximes, a bit higher for 8-PMGO, originates from their particular conformational distribution, in which the phenyloxime aromatic interaction plays a decisive role.

Highly diastereoselective synthesis of 2-azabicyclo[2.2.1]hept-5-ene derivatives: Bronsted acid catalyzed aza-Diels-Alder reaction between cyclopentadiene and imino-acetates with two chiral auxiliaries

The cycloaddition between protonated glyoxylate imines possessing two chiral auxiliaries, N-(S)- or N-(R)-1-phenylethyl and (-)-8-phenylmenthyl or (+)-8-phenylneomenthyl, and cyclopentadiene is described. The absolute configuration of all adducts formed was unequivocally assigned through NMR, specific optical rotation, and X-ray data of appropriated derivatives. Experimental results confirm the highly exo-selectivity for these aza-Diels-Alder reactions, single adducts being obtained from combinations of (8PM)-(R-PEA) and (8PNM)-(S-PEA).

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-