77012-36-3

Upstream product

• 22070-24-2 2,3,4-trimethyltricyclohex-2-en-1-one 
• 36278-54-3 2-(4-methoxyphenyl)ethylmagnesium bromide 
• 77012-32-9 (E)-3-(6-(4-methoxyphenyl)-3-methylhex-3-enyl)-2,2-dimethyloxirane 

Downstream Products

• 113994-60-8 3-(2-p-methoxyphenylethyl)-cis-2,3,4-trimethylcyclohexanol 

Relevant academic research and scientific papers

Diterpene Synthesis. IV Synthesis of Some Octahydrophenanthrenes and a Contribution to the Mechanisms of Cyclialkylations

The cis octahydrophenanthrene (3), a product of the acid-catalysed cyclialkylation of alcohol (1), has been synthesized.Various analogues having cis A/B stereochemistry have also been isolated from cyclization reactions; in these cases there is no rearrangement of the carbon skeleton, as shown by isotopic labelling.Variable temperature n.m.r. studies has been used to define the conformations of some of the cis octahydrophenanthrenes.The mechanisms of cyclialkylations leading to octahydrophenanthrenes can now be clarified.

Cyclisation Reactions: Part VI - Further Study in Biogenetic-type Cyclisation of Epoxy-Olefins

(6E)-9-p-Methoxyphenyl-2,6-dimethylnona-2,6-diene (I) on mono-epoxidation affords mainly 2,3-epoxyolefin (IV) admixed with some 6,7-isomer.IV on cyclisation with boron trifluoride etherate furnishes three ketones: 7-oxo-9-p-methoxyphenyl-2,6-dimethylnon-2-ene (XIII) presumably formed from 6,7-epoxyolefin (XII), cis-3-(2-p-methoxyphenylethyl)-2,2,4-trimethylcyclohexanone (XIV) arising out of 1,4-hydride transfer in an intermediate cyclohexyl cation (XVII), and cis-3-(2-p-methoxyphenylethyl)-2,3,4-trimethylcyclohexanone (XV) resulting from three consecutive 1,2-H, Me shifts in the same intermediate.In addition, 12-methoxypodocarpa-8,11,13-trien-3β-ol (IX) is obtained in 10 percent yield.The mono-epoxide (V) from the corresponding 3-isopropyl-4-methoxyphenyldiene (II) on similar cyclisation affords, among others, hinokiol methyl ether (X) and another crystalline compound characterised by PMR and MS as 12-methoxy-13-isopropyl-A-homo-4a-oxapodocarpa-8,11,13-trien-3β-ol (XXII).The latter is formed by a concerted cyclisation of the di-epoxide (XXI) present in the starting material.Contrary to a previous report from this laboratory, it is now found that trans-podocarpa-8,11,13-trienes (XXV) are more stable than the cis-isomers and are almost the sole products of cyclisation of 2-(2-arylethyl)-1,3,3-trimethylcyclohexyl cations (XXIV) and their analogues under thermodynamically controlled condition.