109182-89-0Relevant academic research and scientific papers
Palladium(0)-catalyzed reaction of propargylic phosphates with SmI2: A highly regioselective route to the synthesis of allenes and acetylenes
Mikami,Mikami, Koichi,Yoshida,Yoshida, Akihiro,Matsumoto,Matsumoto, Shoji,Feng,Feng, Feng,Matsumoto,Matsumoto, Youichi,Sugino,Sugino, Akihiro,Hanamoto,Hanamoto, Takeshi,Inanaga,Inanaga, Junji
, p. 907 - 908 (1995)
A highly regioselective reaction of propargylic phosphates has been established by using SmI2 and a Pd(0) catalyst to give allenes and acetylenes in high isolated yields depending on the substrate used.
Dramatic changeover of regioselectivity in the reduction of propargylic phosphates by palladium(0)/SmI2/proton source system
Yoshida, Akihiro,Mikami, Koichi
, p. 1375 - 1376 (1997)
Regiodivergent synthesis of allenes and acetylenes was established in the reduction of propargylic phosphates. The palladium(0)-catalyzed reduction of secondary propargylic phosphates with samarium(II) iodide gave allenes or acetylenes by tuning proton sources (tert-butyl alcohol or dimethyl L-tartrate).
Trialkylborane-Mediated Propargylation of Aldehydes Using γ-Stannylated Propargyl Acetates
Horino, Yoshikazu,Murakami, Miki,Ishibashi, Mayo,Lee, Jun Hee,Watanabe, Airi,Matsumoto, Rio,Abe, Hitoshi
supporting information, p. 9564 - 9568 (2019/12/24)
A transition-metal-free three-component process that combines aldehydes, 3-(tributylstannyl)propargyl acetates formed in situ from readily available propargyl acetates, and trialkylboranes provides access to a range of 1,2,4-trisubstituted homopropargylic alcohols. The addition of diisopropylamine plays a crucial role in the selective formation of homopropargylic alcohols. Importantly, this methodology can be extended to a single-flask reaction sequence starting from propargyl acetates.
Enantioselective Carbon-Carbon Bond Formation via SN2 Displacements of Acyclic Allylic Mesylates
Marino, Joseph P.,Viso, Alma,Lee, Jae-Don,De La Pradilla, Roberto Fernandez,Fernandez, Paloma,Rubio, M. Belen
, p. 645 - 653 (2007/10/03)
The copper-mediated SN2′ displacement of enantiomerically pure allylic mesyloxy vinyl sulfoxides takes place with high yields and stereoselectivities. In these adducts, the newly created chiral center is adjacent to a vinyl sulfoxide functionality which should allow for subsequent chirality transfer operations. Alternatively, enantiopure alkenyl sulfones and alkenes bearing an allylic stereocenter are readily available from these adducts with high geometric control. The SN2′ displacements of structurally related mesyloxy sulfides and sulfones with organocuprates have been examined. From a single enantiomer at the allylic alcohol position, the absolute configuration of the new chiral center may be controlled by adjusting the oxidation level on sulfur.
Propargylierung von Carbonylverbindungen durch Umpolung von Propargylpalladium-komplexen mit Diethylzink
Tamaru, Yoshinao,Goto, Sachio,Tanaka, Akihiro,Shimizu, Masamichi,Kimura, Masanari
, p. 962 - 963 (2007/10/03)
Keywords: Homopropargylalkohole; Kohlenstoff-Kohlenstoff-Verknuepfungen; Propargylpalladium; Umpolung
Evidence for "stable" organocopper intermediates in the reaction between Me2CuLi·Lil and allylic sulfinyl mesylates
De La Pradilla, Roberto Fernandez,Rubio, M. Belen,Marino, Joseph P.,Viso, Alma
, p. 4985 - 4988 (2007/10/02)
The addition of Me2CuLi·LiI to acyclic allylic sulfinyl mesylates bearing a phenyl functionality in the molecule gives rise to chiral allenes 4 and 11 in variable yields and optical purities, presumably via an unusually stable σ-copper(III) spe
Asymmetric Carbon-Carbon Bond Formation via Sulfoxid-Directed SN2' Displacements of Acyclic Allylic Mesylates
Marino, Joseph P.,Viso, Alma,Pradilla, Roberto Fernandez de la,Fernandez, Paloma
, p. 1349 - 1351 (2007/10/02)
The addition of organocyanocuprates to acyclic allylic mesylates bearing a chiral sulfoxide in the 2-position occurs with complete SN2' regioselectivity, high E/Z stereoselectivity (15:1) and high asymmetric induction to produce enantiomericall
Highly Stereoselective Synthesis of Chiral Alkylallenes by Organocopper(I)-Induced Anti 1,3-Substitution of Chiral Propynyl Esters
Elsevier, Cornelis J.,Vermeer, Peter
, p. 3726 - 3730 (2007/10/02)
The synthesis of chiral 1,3-dialkylallenes R1CH=C=CHR2 of high enantiomeric purity, by applying homogeneous reaction between organocopper(I) reagents of type 2CuX>MgX-LiX> and chiral propynyl methanesulfonates or sulfinates at low temperatures in THF, is reported.The reactions are generally fast; typically complete conversion is obtained within a few minutes at -60 deg C.Overall, high anti stereoselectivity is observed.A plausible mechanism is put forward, and comparison is made with the stereochemistry of reactions of comparable substrates with d10 complexes, e.g. of Pd(0).
REACTIONS OF 3-ALKYL- AND 3,3-DIALKYL-1-BROMOALLENES WITH ORGANOCUPRATES: EFFECTS OF THE NATURE OF THE CUPRATE REAGENT ON THE REGIO- AND STEREOSELECTIVITY
Caporusso, Anna Maria,Polizzi, Carmela,Lardicci, Luciano
, p. 6073 - 6076 (2007/10/02)
Organocuprates induce 1,3- and direct substitution in 3-alkyl- and 3,3-dialkyl-1-bromo-1,2-dienes leading respectively to either terminal acetylenes or allenic hydrocarbons.The nature of the cuprate exerts a prominent role in determining both the regio- and the stereochemistry of these reactions.
A CONVENIENT SYNTHESIS OF ALLENES BY THE REACTION OF PROPARGYL ALCOHOLS WITH GRIGNARD REAGENTS USING 1-CHLORO-2-METHYL-N,N-TETRAMETHYLENEPROPENYLAMINE
Fujisawa, Tamotsu,Iida, Sachio,Sato, Toshio
, p. 4007 - 4010 (2007/10/02)
1-Chloro-2-methyl-N,N-tetramethylenepropenylamine was found to be an efficient condensation reagent for the regioselective coupling reaction of propargyl alcohols with Grignard reagents to give allenes in good yields with high chemo- and enantioselectivities.The utility of the reaction was demonstrated in the stereocontrolled synthesis of methyl (E)-2,4,5-tetradecatrienoate, the pheromone of the male dried bean beetle.
