A one pot synthesis of (E)-4-alkylidene-2-cyclohexen-1-ones

TMSOTf-Catalyzed Stereoselective Isomerization of Acetates of the Baylis - Hillman Adducts

“…[1][2][3][4][5][6] The Baylis-Hillman reaction is an important carbon-carbon bond forming and atom economy reaction, providing a useful class of molecules possessing chemospecific functional groups (Equation 1) which have been successfully used in a variety of stereoselective processes. [7][8][9][10][11][12][13][14][15][16][17][18][19][20] As a part of our research program aimed at the development of the Baylis-Hillman reaction [14][15][16][17][18][19][20] as a source of stereo-selective processes, we herein report trimethylsilyl trifluoromethanesulfonate catalyzed stereoselective isomerization of the acetates of the Baylis-Hillman adducts, i.e. methyl 3-acetoxy-3-aryl-2-methylenepropanoates and 3-acetoxy-3-aryl-2-methylenepropanenitriles into methyl (2E)-2-(acetoxymethyl)-3-arylprop-2-enoates and (2E)-2-(acetoxymethyl)-3-arylprop-2-enenitriles, respectively.…”

The Baylis-Hillman Reaction: One-Pot Stereoselective Synthesis of Methyl (2E)-3-Aryl-2-hydroxymethylprop-2-enoates

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] In continuation of our interest in the development of the Baylis-Hillman reaction as a potential source for stereoselective processes, 9-14 we herein report simple, convenient and one-pot stereoselective transformation of methyl 3-aryl-3-hydroxy-2-methylenepropanoates, the Baylis-Hillman adducts obtained from the activated alkene, methyl acrylate, into methyl (2E)-3-aryl-2-hydroxymethylprop-2-enoates via the successive treatment with acetic anhydride/trimethylsilyl trifluoromethanesulfonate (TMSOTf), and potassium carbonate/methanol in very good yields.(2E)-2-Hydroxymethylalk-2-enoic acids and their esters are useful synthons for synthesis of various biologically active molecules. [15][16][17][18][19][20][21][22] However, there are only a few methods available in the literature for synthesis of these important molecules.…”

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] In continuation of our interest in the development of the Baylis-Hillman reaction as a potential source for stereoselective processes, [9][10][11][12][13][14] we herein report simple, convenient and one-pot stereoselective transformation of methyl 3-aryl-3-hydroxy-2-methylenepropanoates, the Baylis-Hillman adducts obtained from the activated alkene, methyl acrylate, into methyl (2E)-3-aryl-2-hydroxymethylprop-2-enoates via the successive treatment with acetic anhydride/trimethylsilyl trifluoromethanesulfonate (TMSOTf), and potassium carbonate/methanol in very good yields.…”

Et3B-mediated and palladium-catalyzed direct allylation of β-dicarbonyl compounds with Morita–Baylis–Hillman alcohols

“…Later, Chamakh and Amri [38] have described a one-pot synthesis of ( E )-4-alkylidene-2-cyclohexen-1-ones through a cross coupling of the MBH carboxylates with aliphatic 1,3-diketones in the presence of K 2 CO 3 . A drawback of these synthetic approaches is the need to first perform the acylation step of the corresponding allyl MBH alcohols.…”