54315-38-7Relevant articles and documents
Highly Selective Manganese(I)/Lewis Acid Cocatalyzed Direct C?H Propargylation Using Bromoallenes
Zhu, Can,Schwarz, Jonas Luca,Cembellín, Sara,Gre?ies, Steffen,Glorius, Frank
supporting information, p. 437 - 441 (2018/02/21)
A manganese(I)/Lewis acid cocatalyzed direct C?H propargylation with high selectivity has been developed. BPh3 was discovered to not only promote the reactivity, but also enhance the selectivity. Secondary, tertiary, and even quaternary carbon centers at the propargylic position could be directly constructed. Both internal and terminal alkynes are easily accessible. The chirality was successfully transferred from an axially chiral allene to central chirality. The reactivity of the manganese catalyst in this reaction was found to be unique among transition metal catalysts.
Novel, stereoselective and stereospecific synthesis of allenylphosphonates and related compounds via palladium-catalyzed propargylic substitution
Kalek, Marcin,Stawinski, Jacek
supporting information; experimental part, p. 1741 - 1755 (2011/09/15)
We have developed a novel method for the synthesis of allenylphosphonates and related compounds based on a palladium(0)-catalyzed reaction of propargylic derivatives with H-phosphonate, H-phosphonothioate, H-phosphonoselenoate, and H-phosphinate esters. The reaction is stereoselective and stereospecific, and provides a convenient entry to a vast array of allenylphosphonates and their analogues with diverse substitution patterns in the allenic moiety and at the phosphorus center. Some mechanistic aspects of this new reaction were also investigated. Copyright
Synthesis and use of stereospecifically deuterated analogues of palmitic acid to investigate the stereochemical course of the Δ11 desaturase of the processionary moth
Abad, Jose-Luis,Villorbina, Gemma,Fabrias, Gemma,Camps, Francisco
, p. 7108 - 7113 (2007/10/03)
Thaumetopoea pityocampa pheromone glands contain desaturases that, after several sequential reactions from palmitic acid, catalyze the formation of a unique enyne fatty acid, which is the immediate sex pheromone precursor. In this article, we describe the synthesis of different stereospecifically deuterium-labeled and isotopically tagged palmitic acid probes needed to decipher the stereochemical course of the T. pityocampa Δ11 desaturase. The synthesis of probes has been carried out by a chemoenzymatic route, in which the key step is the kinetic lipase-catalyzed resolution of racemic mixtures of secondary propargyl alcohols. The presence of the acetylenic bond simplifies the absolute configuration determination of the resolved alcohols. Moreover, it allows the introduction of the isotopic tag by deuteration. By use of the probes thus prepared, experimental evidence is presented that the Δ11 desaturase of T. pityocampa transforms palmitic acid into (Z)-11-hexadecenoic acid by removal of the pro-(R)-hydrogen atoms from both C11 and C12.
