Mechanism for the Carboxylative Coupling Reaction of a Terminal Alkyne, CO2, and an Allylic Chloride Catalyzed by the Cu(I) Complex: A DFT Study

ACS Catalysis ◽  
2014 ◽  
Vol 4 (12) ◽  
pp. 4466-4473 ◽  
Author(s):  
Ruming Yuan ◽  
Zhenyang Lin
Keyword(s):  
Coupling Reaction ◽  
Dft Study ◽  
Terminal Alkyne ◽  
Allylic Chloride

Convenient Synthesis of (Z)-7- and (E)-9-dodecene-1-yl Acetate, Components of Some Lepidoptera Insect Sex Pheromone

2017 ◽  
Vol 68 (1) ◽  
pp. 180-185
Author(s):  
Adriana Maria Andreica ◽  
Lucia Gansca ◽  
Irina Ciotlaus ◽  
Ioan Oprean
Keyword(s):  
Sex Pheromone ◽  
Coupling Reaction ◽  
Coupling Scheme ◽  
Lithium Aluminium Hydride ◽  
Terminal Alkyne ◽  
Mercury Derivative ◽  
Lithium Aluminium ◽  
Convenient Synthesis ◽  
Practical Synthesis ◽  
Insect Sex

Were developed new and practical synthesis of (Z)-7-dodecene-1-yl acetate and (E)-9-dodecene-1-yl acetate. The routes involve, as the key step, the use of the mercury derivative of the terminal-alkyne w-functionalised as intermediate. The synthesis of (Z)-7-dodecene-1-yl acetate was based on a C6+C2=C8 and C8+C4=C12 coupling scheme, starting from 1,6-hexane-diol. The first coupling reaction took place between 1-tert-butoxy-6-bromo-hexane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-oct-7-yne, which is transformed in di[tert-butoxy-oct-7-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromobutane obtaining 1-tert-butoxy-dodec-7-yne. After acetylation and reduction with lithium aluminium hydride of 7-dodecyne-1-yl acetate gave (Z)-7-dodecene-1-yl acetate with 96 % purity. The synthesis of (E)-9-dodecene-1-yl acetate was based on a C8+C2=C10 and C10+C2=C12 coupling scheme, starting from 1,8-octane-diol. The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromoethane obtaining 1-tert-butoxy-dodec-9-yne. After reduction with lithium aluminium hydride of 1-tert-butoxy-(E)-9-dodecene and acetylation was obtained (E)-9-dodecene-1-yl acetate with 97 % purity.

Unravelling the Mechanism of Glaser Coupling Reaction on Ag(111) and Cu(111) Surfaces: a Case for Halogen Substituted Terminal Alkyne

2018 ◽  
Vol 122 (26) ◽  
pp. 14537-14545 ◽  
Author(s):  
Tao Wang ◽  
Haifeng Lv ◽  
Lin Feng ◽  
Zhijie Tao ◽  
Jianmin Huang ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Terminal Alkyne ◽  
Glaser Coupling

scholarly journals A DFT Study on FeI/FeII/FeIII Mechanism of the Cross-Coupling between Haloalkane and Aryl Grignard Reagent Catalyzed by Iron-SciOPP Complexes

Molecules ◽  
2020 ◽  
Vol 25 (16) ◽  
pp. 3612 ◽  
Author(s):  
Akhilesh Sharma ◽  
Masaharu Nakamura
Keyword(s):  
Density Functional ◽  
Molecular Mechanic ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Dft Study ◽  
Reaction Pathways ◽  
Hydrogen Elimination ◽  
Cross Coupling Reaction ◽  
The Cross ◽  
A Chain

To explore plausible reaction pathways of the cross-coupling reaction between a haloalkane and an aryl metal reagent catalyzed by an iron–phosphine complex, we examine the reaction of FeBrPh(SciOPP) 1 and bromocycloheptane employing density functional theory (DFT) calculations. Besides the cross-coupling, we also examined the competitive pathways of β-hydrogen elimination to give the corresponding alkene byproduct. The DFT study on the reaction pathways explains the cross-coupling selectivity over the elimination in terms of FeI/FeII/FeIII mechanism which involves the generation of alkyl radical intermediates and their propagation in a chain reaction manner. The present study gives insight into the detailed molecular mechanic of the cross-coupling reaction and revises the FeII/FeII mechanisms previously proposed by us and others.

Regiospecific Palladium-Catalyzed Cross-Coupling Reactions Using the Operational Equivalent of 1,3-Dilithiopropyne

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2387-2394 ◽  
Author(s):  
Jorge A. Cabezas ◽  
Natasha Ferllini
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Terminal Alkyne ◽  
Copper Iodide ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
High Yields

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in the presence of catalytic amounts of palladium(0) or (II) and stoichiometric amounts of copper iodide. No terminal alkyne or allene isomers were detected. Reaction conditions were very mild and several functional groups were tolerated.

A DFT Study on the Mechanism of the Coupling Reaction between Chloromethyloxirane and Carbon Dioxide Catalyzed by Re(CO)5Br

2010 ◽  
Vol 29 (9) ◽  
pp. 2069-2079 ◽  
Author(s):  
Cai-Hong Guo ◽  
Jiang-Yu Song ◽  
Jian-Feng Jia ◽  
Xian-Ming Zhang ◽  
Hai-Shun Wu
Keyword(s):  
Carbon Dioxide ◽  
Coupling Reaction ◽  
Dft Study

Synthesis of Fréchet-type Dendrimer Using Glaser-type Coupling Reaction of the Terminal Alkyne-focal Dendrons

2014 ◽  
Vol 597 (1) ◽  
pp. 79-87 ◽  
Author(s):  
Seung Choul Han ◽  
Seung Hwan Kwak ◽  
Seong-Hee Yun ◽  
Sung-Ho Jin ◽  
Jae Wook Lee
Keyword(s):  
Coupling Reaction ◽  
Terminal Alkyne ◽  
Type Coupling
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