Carboxylation of Propargyl Alcohol

Hydroxy group-enabled highly regio- and stereo-selective hydrocarboxylation of alkynes

“…of MeOH in the presence of 2 mol% [PdCl(π-allyl)] 2 , 6 mol% DPEphos, and 5 mol% (PhO) 2 POOH with a CO balloon. Surprisingly, the expected syn -hydrocarboxylation product ( E )- 2a′ 5 was not detected, while 66% of its regioisomeric product ( E )- 2a was exclusively formed unexpectedly together with 25% recovery of 1a (Table 1, entry 1). The regio- and stereo-selectivity were further established by single-crystal X-ray diffraction analysis of ( E )- 2a (Fig.…”

“…, is another feasible way to control regioselectivity through coordination with metal catalysts (Scheme 1d). 4,5 As we know hydrogen bonding interactions have been widely used in organocatalysis,6 and recent publications also demonstrate their capacity in regioselective addition reactions 7. Herein, we report our recent observation on hydroxy group-enabled regioselectivity control in highly stereoselective hydrocarboxylation of readily available 2-alkynylic alcohols affording highly functionalized 3-hydroxy-2( E )-alkenoates (Scheme 1e).…”

Manual of Plastics Analysis

“…112 The acylazide formed rearranges to an amine with the liberation of nitrogen and carbon dioxide 1.6 The carbon dioxide evolved is measured quantitatively by an automatic nonaqueous titration. This method is applicable to poly(m-phenylene isophthalamide) which is soluble in dimethylformamide, but is not applicable to poly (p-phenylene terephthalamide) for which no organic solvent could be found.…”

New insights into the alkoxycarbonylation of propargyl alcohol

“…In particular, earlier studies on the transition-metal catalyzed alkoxycarbonylation of propargyl alcohol (see Scheme 1) and its derivatives can be traced back to 1950s [7][8][9], when pioneering experiments were carried out employing Ni(CO) 4 either in stoichiometric or in catalytic fashion [10][11][12][13][14][15].…”