76320-22-4Relevant academic research and scientific papers
Synthesis of 3-substituted 2-cyclohexenones through umpoled functionalization
Lechuga-Eduardo, Harim,Zarza-Acu?a, Eduardo,Romero-Ortega, Moisés
, p. 3234 - 3237 (2017/07/27)
A new protocol to obtain 3-substituted 2-cyclohexenones, was developed by reversing the chemical reactivity of 2-cyclohexenone. One-pot synthesis of 3-substituted 2-cyclohexenones can be achieved by treatment of 3-phenylthiosilyl enol ether with a mixture of t-BuLi/HMPA that allows hydrogen-selective exchange in presence of reactive electrophiles such as aldehydes, ketones and alkyl halides. This affords the corresponding product in moderate overall yield, after silyl enol ether cleavage and concomitant thiophenol elimination initiated with TBAF.
Synthesis of Functionalized Ring C of Escobarines
Lechuga-Eduardo, Harim,Romero-Ortega, Moises,Olivo, Horacio F.
, p. 51 - 54 (2016/01/20)
A synthetic strategy was developed for the preparation of α-ethynyl-α,β-epoxy-β-formyl- and α-ethynyl-α,β-epoxy-β-(hydroxymethyl)cyclohexanone from cyclohexenone as a model study in a proposed synthesis of escobarines. This highly functionalized ring is f
Synthesis of an epoxyquinol analog: Efficient methodology for the insertion of side chains into cyclohexenone cores
Heguaburu, Viviana,Schapiro, Valeria,Pandolfi, Enrique
scheme or table, p. 6921 - 6923 (2011/02/27)
A novel epoxyquinol analog was prepared by molecular simplification of monomeric and dimeric scaffolds. A feasible methodology for the insertion of side chains into cyclohexenone skeleton was developed. Insertion of the hydroxymethyl side chain was achiev
Studies on the substituted 3-aminopropan-1-ol motif of lycoctonine class norditerpenid alkaloids: A novel route to 3-hydroxymethylcyclohex-2-enone
Doisy, Xavier,Blagbrough, Ian S.,Thomas, Noel F.,Potter, Barry V. L.
, p. 8525 - 8528 (2007/10/03)
Pursuing our interest in methyllcaconitine (MLA), we have designed a synthetic route to substituted ring-A of lycoctonine class norditerpenoid alkaloids. A novel synthesis of 3-hydroxymethylcyclohex-2-enone has been achieved starting from cyclohex-2-enone. Key reactions are: 1,2-addition of 1,3-dithiane followed by allylic rearrangement, 1,4-hydrocyanation, Wittig reaction and conversion into the substituted N-ethyl-3-aminopropan-1-ol motif of these neopentyl-like alcohols.
A tandem Horner-Emmons olefination-gonjugate addition approach to the synthesis of 1,5-Disubstituted-6-azabicyclo[3.2.1]octanes based on the AE ring structure of the norditerpenoid alkaloid methyllycaconitine
Callis, David J.,Thomas, Noel F.,Pearson, David P. J.,Potter, Barry V. L.
, p. 4634 - 4640 (2007/10/03)
A novel Horner-Emmons olefination conjugate addition reaction of N-acetylamides to form 1,5-disubstituted-6-azabicyclo[3.2.1]octanes with two bridgehead quarternary carbon centers is reported. This reaction is a key step in an approach to the synthesis of small ring analogues based on the AE ring structure of the Delphinium norditerpenoid, methyllycaconitine (MLA) (1). Initially, 3-(hydroxymethyl)cyclohex-2-en-1-one (10) was selected as the starting material to these structures, but its generation proved inefficient. In contrast, the synthesis of 3-[(phenylthio)methyl]cyclohex-2-en-1-one (6) and 3-(1,3-dithian-2-yl)cyclohex-2-en-1-one (11) proceeded in good yield. Subsequent hydrocyanation, ketalization, reduction, acetylation, deprotection of the acetal, and Horner-Emmons olefination-conjugate addition reaction to form 1-[(phenylthio)methyl]-5-[(ethoxycarbonyl)methyl]-6-acetamido-6-azabicyclo[3.2. 1]octane(28), 1-(1,3-dithian-2-yl)-5-[(ethoxycarbonyl)methyl]-6-acetyl-6-azabicyclo[3.2.1] octane (29), respectively, are reported, as well as for readily available 3-methylcyclohex-2-en-1-one (12). Studies on the Pummerer rearrangement of 28 and subsequent desulfurization and reduction to form an hydroxymethyl-substituted azabicyclo[3.2.1.]octane (40) and then selective protection to form a protected hydroxyethyl N-ethyl (hydroxymethyl)azabicyclo-[3.2.1]octane (3) are also described.
Regiochemistry of the Intramolecular Photocycloaddition of Enones to Vinyl Ethers as a Function of Chain Length
Gleiter, Rolf,Fischer, Evelyn
, p. 1899 - 1912 (2007/10/02)
The intramolecular cycloaddition of a cyclohexenone moiety bound to a vinyl ether fragment has been explored.The regiochemistry and the quantum yield of the reaction has been investigated as a function of the chain length n and the position of the methoxy group.It has been found that in those cases where the chain consists of three and four members the position of the methoxy group has no influence on the regiochemistry but on the quantum yield.Only head-to-head cycloaddition is observed.In the case of n = 2 both the regiochemistry and the quantum yield depend strongly on the position of the methoxy group.It is concluded that the main reason for the different behavior of n = 2 is due to a through-bond effect between the two olefinic units mediated by a C2H4 bridge. Key Words: Rule of five / Photocycloaddition / Regiochemistry / Enones / Vinyl ethers
