81002-23-5

Upstream product

• 109-72-8 n-butyllithium 
• 81002-19-9 (1'R,2'S,5'R)-2'-(2''-phenylpropan-2''-yl)-5'-methylcyclohexyl (E)-but-2-enoate 
• 10352-88-2 E-hept-2-enoic acid 
• 65253-04-5 (-)-8-phenylmenthol 
• 917-54-4 methyllithium 
• 81002-21-3 (E)-Hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 81002-20-2 (+)-8-phenylmenthyl Z-crotonate 

Downstream Products

• 59614-85-6 (-)-(S)-3-methylheptanoic acid 
• 65253-04-5 (-)-8-phenylmenthol 
• 169136-81-6 (-)-(1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl tetrolate 
• 81002-20-2 (+)-8-phenylmenthyl Z-crotonate 
• 81002-21-3 (E)-Hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 

Relevant academic research and scientific papers

ASYMMETRIC 1,4-ADDITIONS OF COORDINATED MeCu.BF3 TO CHIRAL ENOATES: ENANTIOSELECTIVE SYNTHESES OF (S)-(-)-CITRONELLIC ACID

nBu3P- or cyanide-stabilized RCu.BF3 (R=Me, 4-Me-3-pentenyl) undergo efficient 1,4-additions to neopentylether-shielded trans-enoates.Thus chiral β-substituted carboxylic acids e.g. (S)-citronellic acid were obtained in high e.e. (Schemes 2 and 4).

High Asymmetric Induction in Conjugate Additions of RCu*BF3 to Chiral Enoates

1,4-Additions of PhCu*BF3, n-BuCu*BF3 and MeCu*BF3 to the trans-8-phenylmenthyl enoates 1 proceeded with high chiral induction.Saponification of the resulting esters 2 gave the corresponding enantiomerically pure β-substituted alkanoic acids 3 and the recovered (-)-8-phenylmenthol in good overall yields.Analogous additions to the cis-crotonate 1 led preferentially to the acids 3 enantiomeric to those obtained from the trans-crotonate 1, although with lower selectivity.A stereochemical model is proposed consistent with the observed results (Scheme 2, Table).