78523-40-7Relevant academic research and scientific papers
A novel cis-selective cyclohexanone annulation as the key step of a total synthesis of the sesquiterpene lsoacanthodoral
Hampel, Thomas,Brueckner, Reinhard
supporting information; experimental part, p. 4842 - 4845 (2010/03/03)
Isoacanthodoral (1) Is a structurally unique sesquiterpene in that it is a bicyclo[4.4.0]dec-1-ene with a cis- rather than the common transjunction between the constituting rings. An efficient construction of this motif has been accomplished by a novel ci
Synthesis based on cyclohexadienes. Part 23. Total synthesis of 5-epi-pupukean-2-one
Kaliappan, Krishna,Subba Rao
, p. 3387 - 3392 (2007/10/03)
A new strategy for the construction of the isotwistane skeleton is reported from easily available cyclohexadienes which involves stereoselective alkylation of a bicyclooctenone derivative and a decarboxylative 5-exo-trig radical cyclisation as the key ste
Uncatalyzed Sigmatropic 1,5-Shift of Acyl Groups in the Thermolysis of 5-Acyl-5-methyl-1,3-cyclohexadienes
Schiess, Peter,Dinkel, Rolf,Fuenfschilling, Peter
, p. 787 - 800 (2007/10/02)
Four different 5-acyl-5-methyl-1,3-cyclohexadienes 1a-d (R=COOCH3, COCH3, COC6H5, CHO) have been shown to yield mixtures of 1,3-disubstituted cyclohexadienes 2-7 and 1,3-disubstituted aromatic product 8 upon thermolysis at 150-300 deg C in solution and at 350-500 deg C in the gas phase in a flow system.Two reaction pathways are considered for the rearrangement of the C-Skeleton.For the ester 1a 13C-isotopic substitution shows that products arise to 75-86percent through a 1,5-sigmatropic shift of the methoxycarbonyl group and to 14-25percent through a sequence of reaction steps involving a 1,7-H-shift reaction in an acyclic intermediate.For the more reactive compounds 1b-d isomerization is assumed to follow the 1,5-sigmatropic pathway exclusively.A kinetic study yields the following sequence for the migration tendency of acyl groups toward sigmatropic 1,5-shift: COOCH3 COCH3 COC6H5 CHO.
