54154-45-9

Upstream product

• 488787-28-6 4-[(1-methyl-1-triethylsilyloxy)ethyl]-2-cyclohexen-1-one 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 52691-72-2 (-)-Apoverbenone 
• 77982-63-9 nopinone 
• 127-91-3 (1R,5R)-(+)-β-pinene 
• 75-16-1 methylmagnesium bromide 
• 17015-63-3 (S,E)-1-(3,7-dimethyl-3-vinylocta-1,6-dien-1-yl)-4-methoxybenzene 

Downstream Products

• 54154-46-0 2-[(1S,2S,4R)-2-(4-Methoxy-phenyl)-4-methyl-4-vinyl-cyclohexyl]-2-methyl-oxirane 
• 54154-48-2 1-((1S,2R,5R)-2-Isopropyl-5-methyl-5-vinyl-cyclohexyl)-4-methoxy-benzene 
• 54154-50-6 1-((R)-2-Isopropyl-5-methyl-5-vinyl-cyclohex-1-enyl)-4-methoxy-benzene 

Relevant academic research and scientific papers

Further study on synthesis of the cyclobakuchiols

Abstract Two results are described. First, quinic acid was transformed into the monoacetate of 2-cyclohexene-1,4-diol. The Ni-catalyzed allylic substitution of the monoacetate with CH2C(Me)MgBr/ZnCl2/TMEDA followed by oxidation of th

Synthesis of cyclobakuchiols A, B, and C by using conformation-controlled stereoselective reactions

Cyclohexanone with the pMeOC6H4 and CH 2/C(Me) substituents at the C3 and C4-positions was prepared from (+)-β-pinene and converted to the allylic picolinate by a Masamune-Wittig reaction followed by reduction and esterification. Allylic substitution of this picolinate with Me2CuMgBr×MgBr2 in the presence of ZnI2 proceeded with γ regio- and stereoselectively to afford the quaternary carbon center on the cyclohexane ring with the CH2/CH and Me groups in axial and equatorial positions, respectively. This product was converted to cyclobakuchiol A by demethylation and to cyclobakuchiol C by epoxidation of the CH2/C(Me) group. For the synthesis of cyclobakuchiol B, the enantiomer of the above cyclohexanone derived from (-)-β-pinene was converted to the cyclohexane-carboxylate, and the derived enolate was subjected to the reaction with CH2/CHSOPh followed by sulfoxide elimination to afford the intermediate with the quaternary carbon center with MeOC(/O) and CH2/CH groups in axial and equatorial positions. The MeOC(/O) group was transformed to the Me group to complete the synthesis of cyclobakuchiol B. Control is key! Synthesis of cyclobakuchiols A and C was stereoselectively accomplished by conformation-controlled substitution of allylic picolinate with Me2CuMgBr×MgBr2/ZnI 2. On the other hand, cyclobakuchiol B was synthesized by stereoselective addition of the cyclohexanecarboxylate enolate to CH 2/CHSOPh (see scheme). Copyright