13277-92-4

Upstream product

• 80-59-1 Tiglic acid 
• 106-99-0 buta-1,3-diene 
• 591-49-1 1-methylcyclohex-1-ene 
• 7077-04-5 2-methyl-1-cyclohexanecarboxylic acid 
• 74-88-4 methyl iodide 
• 13277-91-3 (+/-)-cis-1.2-Dimethyl-cyclohexen-⁽⁴⁾-carbonsaeure-⁽¹⁾ 
• 5402-29-9 1,2-dimethylcyclohexanol 
• 139894-31-8 (2R,3S)-3-carbomethoxy-2,3-dimethylcyclohexan-1-one 
• 139760-69-3 (1S,2R,3S)-3-carbomethoxy-2,3-dimethyl-1-hydroxycyclohexane 
• 139894-33-0 (1S,2S)-1-carbomethoxy-1,2-dimethylcyclohexane 

Downstream Products

• 115588-50-6 (1S,2S)-1,2-dimethyl-1-acetylcyclohexane 
• 13366-79-5 (+/-)-1,2t-dimethyl-cyclohex-r-ylamine 
• 73873-46-8 methyl 1-methyl-trans-2-methylcyclohexanecarboxylate 
• 1122-02-7 1-chloro-1,2-dimethyl-cyclohexane 

Relevant academic research and scientific papers

Diastereoselective ester enolate alkylations. Asymmetric syntheses of 3-alkyl-3-carbomethoxy-2-exo-methylenecyclohex-5-en-1-ones

Enolate 12, designed to take advantage of potential chelation sites on the chiral auxiliary, (S)-2-(methoxymethyl)pyrrolidine, gives excellent diastereoselectivities for alkyl-, propargyl-, and cyanomethylations; negligible diastereoselectivities were observed for allyl- and benzylations. The resulting 3-substituted 3-carbomethoxy-1,4-cyclohexadienes 3a-g were converted to 3-substituted 3-carbomethoxy-2-exo-methylenecyclohex-5-en-1-ones 4a-g. Experiments designed to detect the possible involvement of single-electron transfer during alkylation of enolate 12 indicate that alkylations most probably occur via the SN2 pathway.

Stereochemistry of Alkylation of Carboxylic Acid Salt and Ester α Anions Derived from Cyclic Systems.

A stereochemical study of the alkylation of α-lithiated carboxylate salts and esters has been performed.The α anions derived from the bicyclic acids exo-1, endo-1, and 7 (R=H) and the esters 4 and 7 (R=CH3) yield predominantly exo alkylation.As an example, the α anion derived from ester 7 (R=CH3) on treatment with CH3I yields exo-8 (R=R'=CH3) and endo-9 (R=R'=CH3) in a 97:3 ratio, a highly stereoselective reaction.Addition of TMEDA to the reactions involving the α anions derived from exo- or endo-1 did not change the stereochemical alkylation results.The α anions derived from the substituted cyclohexanecarboxylic acids 10, 13, 16, 19, or 22 (where R=H in each case) on methylation yield more axial methylation (axial/equatorial ratios of 0.4-2.7) than the α anions derived from the methyl esters corresponding to these acids.The α anions from the esters yield predominantly equatorial methylated products (e/a ratios varying from 4 to 9).The reasons for the different stereochemical results are discussed.