High-pressure initiated synthesis of dominicalures 1 and 2 by the Baylis-Hillman method

Phosphinic Acid Pseudopeptides Analogous to Glutamyl-γ-glutamate: Synthesis and Coupling to Pteroyl Azides Leads to Potent Inhibitors of Folylpoly-γ-glutamate Synthetase

“…All other reagents were purchased from Sigma-Aldrich and were used without further purification. n -Octylphosphinic acid 6 (R 2 = (CH 2 ) 6 CH 3 ) and 2-[(hydroxyphosphinyl)methyl]pentane-1,5-dioic acid dibenzyl ester 6 (R 2 = CH(CO 2 Bn)CH 2 CH 2 CO 2 Bn) were prepared using methods previously described. ,, The dibenzyl and dimethyl esters of 2-methyleneglutarate were prepared by literature procedures. , With minor modifications, pteroylhydrazide 40 and the 4-amino-4-deoxy-10-methyl analogue of pteroic acid were synthesized as described previously. Experimental details, including complete spectral characterization, for the synthesis of these two precursors of azides 13a and 13b are contained in the Supporting Information.…”

Dimerization of Methyl Acrylate through CO2‐pressurized DBU Mediated Process

“…Easily made from very cheap raw materials and produced on a vast industrial scale, the use of such inexpensive acrylic compound as starting substrate in organic synthesis is of particular interest. Today plethora of synthetic methods used in converting MA in usable products, including polymers, have been reported [1–7] but data on its dimerization are rare [8–12] . The head‐to‐tail MA dimer, i. e .…”

“…According to reported data, [11,17,18] 1,4‐diazabicyclo[2.2.2]octane (DABCO) is an efficient catalyst for the Baylis‐Hillman reaction but is unactive for the dimerization of methyl acrylate in a Rauhut‐Currier process. Interestingly, Aggarwal and Mereu demonstrated that DBU is actually the optimum organic catalyst for the Baylis‐Hillman reaction, providing adducts at much faster rates than using DABCO [19] .…”

“…As observed by Zhulin et al . who studied the dimerization of MA by the action of tri(n‐butyl)phosphine in the absence of solvent, [11] the effectiveness of the bimolecular process at the first stage is sharply increased by the use of a high‐pressure technique. To that reason, three different CO 2 pressures (1, 20 and 40 bars) were evaluated for the synthesis of DMG ([MA] 0 /[DBU] 0 =1, 23 °C).…”

“…Today plethora of synthetic methods used in converting MA in usable products, including polymers, have been reported [1][2][3][4][5][6][7] but data on its dimerization are rare. [8][9][10][11][12] The head-to-tail MA dimer, i. e. dimethyl α-methyleneglutarate (DMG, Figure 1), is the smallest representative of saturated branched MA dimers. Already studied for its radical polymerization ability, [13][14][15] DMG offers interest and new perspectives in material science in the same way as the 2-ethylidene-3-methylpentanedioates recently prepared by dimerization of crotonates providing a sustainable route to difunctional monomers for step-growth polymerizations.…”