Pd-catalyzed cross-coupling of terminal alkynes with ene-yne-ketones: access to conjugated enynes via metal carbene migratory insertion

2015 ◽  
Vol 51 (56) ◽  
pp. 11233-11235 ◽  
Author(s):  
Ying Xia ◽  
Zhen Liu ◽  
Rui Ge ◽  
Qing Xiao ◽  
Yan Zhang ◽  
...  
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Terminal Alkynes ◽  
Conjugated Enynes ◽  
Migratory Insertion ◽  
Insertion Process

Pd-catalyzed oxidative cross-coupling of terminal alkynes with ene-yne-ketones has been developed, in which the ene-yne-ketones are served as carbene precursors and metal carbene migratory insertion process is the key step for C–C bond formation.

Palladium-catalyzed denitrative Sonogashira-type cross-coupling of nitrobenzenes with terminal alkynes

2020 ◽  
Vol 56 (5) ◽  
pp. 790-793 ◽  
Author(s):  
Boya Feng ◽  
Yudong Yang ◽  
Jingsong You
Keyword(s):  
Bond Formation ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Terminal Alkynes ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed

Described herein is a palladium-catalyzed cross-coupling reaction between nitroarenes and terminal alkynes, offering a facile method for C(sp2)–C(sp) bond formation.

RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes

2015 ◽  
Vol 68 (9) ◽  
pp. 1379 ◽  
Author(s):  
Zhen Liu ◽  
Ying Xia ◽  
Sheng Feng ◽  
Shuai Wang ◽  
Di Qiu ◽  
...  
Keyword(s):  
Diazo Compound ◽  
Cross Coupling ◽  
Mild Conditions ◽  
Alternative Approach ◽  
Migratory Insertion ◽  
Type Coupling ◽  
Insertion Process ◽  
Coupling Partner

A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI–carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

scholarly journals Selective Manganese-Catalyzed Dimerization and Cross-Coupling of Terminal Alkynes

2021 ◽  
Author(s):  
Stefan Weber ◽  
Luis F. Veiros ◽  
Karl Kirchner
Keyword(s):  
Dft Calculations ◽  
Precious Metal ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Metal Catalyst ◽  
Catalyst Loading ◽  
Terminal Alkynes ◽  
Migratory Insertion ◽  
Earth Abundant ◽  
First Time

<div>For the first time, an efficient manganese-catalyzed dimerization of terminal alkynes to afford 1,3-enynes is described. This reaction is atom economic, implementing an inexpensive, earth abundant non-precious metal catalyst. The pre-catalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid C-H bond cleavage of the alkyne forming an active Mn(I) acetylide catalyst [Mn(dippe)(CO)2(C≡CPh)(η2-HC≡CPh)] together with liberated butanal. A range of aromatic and aliphatic terminal alkynes were efficiently and selectively converted into head-to-head Z-1,3-enynes and head-to-tail gem-1,3-enynes, respectively, in good to excellent yields. Moreover, cross-coupling of aromatic and aliphatic alkynes yields selectively head-to-tail gem-1,3-enynes. In all cases, the reactions were performed at 70 °C with a catalyst loading of 1-2 mol %. A mechanism based on DFT calculations is presented.</div><div><br></div>

scholarly journals Selective Manganese-Catalyzed Dimerization and Cross-Coupling of Terminal Alkynes

2021 ◽  
Author(s):  
Stefan Weber ◽  
Luis F. Veiros ◽  
Karl Kirchner
Keyword(s):  
Dft Calculations ◽  
Precious Metal ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Metal Catalyst ◽  
Catalyst Loading ◽  
Terminal Alkynes ◽  
Migratory Insertion ◽  
Earth Abundant ◽  
First Time

<div>For the first time, an efficient manganese-catalyzed dimerization of terminal alkynes to afford 1,3-enynes is described. This reaction is atom economic, implementing an inexpensive, earth abundant non-precious metal catalyst. The pre-catalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes rapid C-H bond cleavage of the alkyne forming an active Mn(I) acetylide catalyst [Mn(dippe)(CO)2(C≡CPh)(η2-HC≡CPh)] together with liberated butanal. A range of aromatic and aliphatic terminal alkynes were efficiently and selectively converted into head-to-head Z-1,3-enynes and head-to-tail gem-1,3-enynes, respectively, in good to excellent yields. Moreover, cross-coupling of aromatic and aliphatic alkynes yields selectively head-to-tail gem-1,3-enynes. In all cases, the reactions were performed at 70 °C with a catalyst loading of 1-2 mol %. A mechanism based on DFT calculations is presented.</div><div><br></div>

5-Iodo-1H-1,2,3-triazoles as Versatile Building Blocks

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1874-1896 ◽  
Author(s):  
Irina A. Balova ◽  
Natalia A. Danilkina ◽  
Anastasia I. Govdi
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Building Blocks ◽  
Terminal Alkynes ◽  
Direct Arylation ◽  
Halogen Exchange ◽  
The Creation ◽  
Radiolabeled Compounds ◽  
Synthetic Approaches ◽  
Synthetic Application

Copper-catalyzed azide–alkyne cycloaddition is a useful tool for the synthesis of both 1,2,3-triazoles and 5-iodo-1H-1,2,3-triazoles starting from either terminal alkynes or iodoalkynes. 5-Iodotriazoles have been recognized as very useful building blocks for the synthesis of diverse 1,4,5-trisubstituted 1,2,3-triazoles. Synthetic application of 5-iodo-1,2,3-triazoles through the creation of a new C–C, C–heteroatom, or C–D(T) bond along with the application areas of both iodotriazoles and products of their modification including radiolabeled compounds are discussed.1 Introduction2 Synthetic Approaches to 5-Iodo-1H-1,2,3-triazoles3 5-Iodotriazoles in C–C Bond Formation3.1 Intermolecular C–C Cross-Coupling3.2 Intramolecular Cross-Coupling: Direct Arylation and C–I/C–I Homocoupling­3.3 Other Transformations4 5-Iodotriazoles in Radiolabeling, Halogen Exchange, and Heterocoupling Reactions5 Summary

Palladium-Catalyzed Oxidative Cross-Coupling of N-Tosylhydrazones or Diazoesters with Terminal Alkynes: A Route to Conjugated Enynes

2011 ◽  
Vol 123 (15) ◽  
pp. 3572-3576 ◽  
Author(s):  
Lei Zhou ◽  
Fei Ye ◽  
Jiachen Ma ◽  
Yan Zhang ◽  
Jianbo Wang
Keyword(s):  
Cross Coupling ◽  
Terminal Alkynes ◽  
Conjugated Enynes ◽  
Palladium Catalyzed

scholarly journals Atom-Economical Cross-Coupling of Internal and Terminal Alkynes to Access 1,3-Enynes

2020 ◽  
Author(s):  
Mingyu Liu ◽  
Tianhua Tang ◽  
Omar Apolinar ◽  
Rei Matsuura ◽  
Carl Busacca ◽  
...  
Keyword(s):  
Chemical Synthesis ◽  
Large Scale ◽  
Bond Formation ◽  
Cross Coupling ◽  
Building Blocks ◽  
Commercial Production ◽  
Catalytic Cycle ◽  
Catalyst Loading ◽  
Terminal Alkynes ◽  
Catalytic Method

Selective carbon–carbon (C–C) bond formation in chemical synthesis generally requires pre-functionalized building blocks. However, the requisite pre-functionalization steps undermine the efficiency of multi-step synthetic sequences, which is particularly problematic in large-scale applications, such as in the commercial production of pharmaceuticals. Herein, we describe a selective and catalytic method for synthesizing 1,3-enynes without pre-functionalized building blocks. This method is facilitated by a tailored P,N-ligand that enables regioselective coupling and suppresses secondary <i>E</i>/<i>Z</i>-isomerization of the product. The transformation enables several classes of unactivated internal acceptor alkynes to be coupled with terminal donor alkynes to deliver 1,3-enynes in a highly regio- and stereoselective manner. The scope of compatible acceptor alkynes includes propargyl alcohols, (homo)propargyl amine derivatives, and (homo)propargyl carboxamides. The reaction is scalable and can operate effectively with 0.5 mol% catalyst loading. The products are versatile intermediates that can participate in various downstream transformations. We also present preliminary mechanistic experiments that are consistent with a redox-neutral Pd(II) catalytic cycle.

Sign in / Sign up

Export Citation Format

Share Document