75946-01-9

Upstream product

• 75946-00-8 5-Benzoyl-2-oxo-5-phenyl-cyclohexancarbonsaeure 
• 75945-98-1 5-Benzoyl-2-oxo-5-phenyl-cyclohexancarbonsaeureethylester 
• 75945-99-2 5-Benzoyl-2-oxo-5-phenyl-cyclohexancarbonsaeurebenzylester 
• 103924-00-1 4-benzoyl-4-phenyl-heptanedioic acid 

Downstream Products

• 103924-13-6 (1S,3S,5S,6R,7S,9R)-6-Hydroxy-9-methyl-6,7-diphenyl-adamantane-2,4-dione 
• 103924-13-6 (1S,3S,5S,6R,7S)-6-Hydroxy-9-methyl-6,7-diphenyl-adamantane-2,4-dione 
• 103924-13-6 (1R,3R,5R,6R,7R)-6-Hydroxy-9-methyl-6,7-diphenyl-adamantane-2,4-dione 
• 75946-02-0 3,4-Diphenyl-2-azabicyclo<2.2.2>octan 
• 75946-04-2 2-Benzyl-3,4-diphenyl-2-azabicyclo<2.2.2>octan 
• 75946-03-1 2-Methyl-3,4-diphenyl-2-azabicyclo<2.2.2>octan 
• 103924-10-3 1-phenyl-4-pyrrolidin-1-ylcyclohex-3-enyl phenyl ketone 

Relevant academic research and scientific papers

Enamine Chemistry. Part 29. Synthesis of Adamantane Derivatives from α,β-Unsaturated Acid Chlorides and 4,4-Disubstituted Cyclohexanone Enamines. Multiple Sigmatropic Rearrangement Transition State Stereochemistry. X-Ray analysis

Chemical, spectroscopic and X-ray crystallographic evidence has confirmed that the three isomers of 6-hydroxy-7,9-dimethyl-6-phenyladamantane-2,4-dione, obtained by the reaction of crotonoyl chloride with the pyrrolidine enamine of 4-benzoyl-4-methylcyclohexanone, have the 9α-methyl-6α-phenyl (4), 9β-methyl-6α-phenyl (2), and 9β-methyl-6β-phenyl (3) configurations.The mechanism of their formation has been investigated and the evidence available indicates that the stereochemistry of the C-6 and C-9 chiral centres is determined largely by the stereochemistry of the sigmatropic rearrangement leading to them.A chair-like transition state for the rearrangement, occuring from the same side of the cyclohexene ring as the benzoyl group (chair-syn) in the intermediate N-acylated enamine (9a) must lead to the 9α-Me, 6α-Ph configuration as in (4), whereas the same process from the opposite side (chair-anti) followed by inversion of the substituted ring carbon could lead to the 9β-Me, 6α-Ph configuration as in (2) and the 9β-Me, 6β-Ph configuration as in (3).Howerer, the main isomer (3), having the more crowded 9β-Me, 6β-Ph configuration, is more likely to be derived by a sigmatropic rearrangement having a boat-like transition state, but again occuring from the same side of the cyclohexene ring as the benzoyl group (boat-syn).An X-ray crystallographic analysis of 6β-hydroxy-7,9α-dimethyl-6α-phenyladamantane-2,4-dione (4) and of 3-(5-benzoyl-5-methyl-2-oxocyclohexyl)-butanoic acid (34), isolated at an intermediate stage in the above reaction, has been carried out.The corresponding reaction of αβ-unsaturated acid chlorides with enamines of 4-benzoyl-4-phenyl-cyclohexanone (9c) and ethyl 1-benzoyl-4-oxocyclohexane-1-carboxylate (9b) has been carried out and shown to lead to 6-hydroxy-6,7-diphenyladamantane-2,4-diones and ethyl 2-hydroxy-4,6-dioxo-2-phenyladamantane-1-carboxylates respectively, as a mixture of stereoisomers.A similar multiplicity in the stereochemistry of the transition state of the sigmatropic rearrangement is evident from the structures of the adamantane derivatives produced.

Synthesis and Reactivity of 4-Phenylisoquinuclidines

Several approaches to the synthesis of the 2-alkyl-4-phenylisoquinuclidines 14 and 15, the 3,4-diphenylisoquinuclidines 22-24 and of 6-oxo-4-phenyl-3-isoquinuclidone (43) are described.The structure of the products of hydrolysis of 7-phenyl-1,4-dioxaspirodecanecarboxamide (36) were determined by spectroscopy and degradative reactions.