Directed C–C bond cleavage of a cyclopropane intermediate generated fromN-tosylhydrazones and stable enaminones: expedient synthesis of functionalized 1,4-ketoaldehydes

2017 ◽  
Vol 53 (91) ◽  
pp. 12286-12289 ◽  
Author(s):  
Meiyan Ni ◽  
Jianguo Zhang ◽  
Xiaoyu Liang ◽  
Yaojia Jiang ◽  
Teck-Peng Loh
Keyword(s):  
Efficient Method ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Quaternary Centers

An efficient method to construct functionalized 1,4-ketoaldehydes bearing all-carbon α-quaternary centersviaregioselective C–C bond activation has been described.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

scholarly journals The Exchange of Cyclometalated Ligands

Molecules ◽  
2021 ◽  
Vol 26 (1) ◽  
pp. 210
Author(s):  
Alexander D. Ryabov
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Cyclopalladated Complexes ◽  
Derivatives Of ◽  
Cyclometalated Ligand ◽  
Incoming Ligand

Reactions of cyclometalated compounds are numerous. This account is focused on one of such reactions, the exchange of cyclometalated ligands, a reaction between a cyclometalated compound and an incoming ligand that replaces a previously cyclometalated ligand to form a new metalacycle: + H-C*~Z ⇄ + H-C~Y. Originally discovered for PdII complexes with Y/Z = N, P, S, the exchange appeared to be a mechanistically challenging, simple, and convenient routine for the synthesis of cyclopalladated complexes. Over four decades it was expanded to cyclometalated derivatives of platinum, ruthenium, manganese, rhodium, and iridium. The exchange, which is also questionably referred to as transcyclometalation, offers attractive synthetic possibilities and assists in disclosing key mechanistic pathways associated with the C–H bond activation by transition metal complexes and C–M bond cleavage. Both synthetic and mechanistic aspects of the exchange are reviewed and discussed.

Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Synthesis ◽  
2021 ◽  
Author(s):  
Wey-Chyng Jeng ◽  
Po-Chung Chien ◽  
Sandip Sambhaji Vagh ◽  
Athukuri Edukondalu ◽  
Wenwei Lin
Keyword(s):  
Intramolecular Cyclization ◽  
Efficient Method ◽  
Bond Cleavage ◽  
Scale Up ◽  
Acyl Chlorides ◽  
Metal Free ◽  
Mild Conditions ◽  
Synthetic Utility ◽  
Mechanistic Investigations ◽  
Synthetic Transformations

We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides in the presence of base-catalyzed by organophosphanes. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under metal-free and mild conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/ rearrangement sequence. The mechanistic investigations revealed that the C-O bond cleavage on possible betaine intermediate is the key step for the installation of keto-functionality at β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by scale-up reactions and synthetic transformations of the products.

scholarly journals Carbon-Hydrogen Bond Activation of Phenyldi(2- Thienyl)Phosphine at A Triruthenium Cluster Center

2012 ◽  
Vol 25 (1) ◽  
pp. 1-6 ◽  
Author(s):  
Shahed Rana ◽  
Shishir Ghosh ◽  
Shariff E Kabir
Keyword(s):  
Hydrogen Bond ◽  
Elemental Analysis ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Chemical Society ◽  
Cluster Center ◽  
Carbon Hydrogen Bond Activation

Ketyl-initiated reaction between Ru3(CO)12 and phenyldi(2-thienyl)phosphine (PhPTh2) furnished simple phosphine-substituted triruthenium clusters [Ru3(CO)10(PhPTh2)21 and [Ru3(CO)9(PhPTh2)3] 2. Heating 1 in boiling benzene afforded [Ru3(CO)8{?3- PhThP(C4H2S)}(PhPTh2)] 3 by carbon-hydrogen bond cleavage of a coordinated thienylphosphine ligand. All three new clusters have been characterized by elemental analysis, IR and NMR spectroscopic data.DOI: http://dx.doi.org/10.3329/jbcs.v25i1.11764 Journal of Bangladesh Chemical Society, Vol. 25(1), 1-6, 2012

scholarly journals Steric C–N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2

2015 ◽  
Vol 51 (92) ◽  
pp. 16468-16471 ◽  
Author(s):  
Yan X. Shi ◽  
Rong Z. Liang ◽  
Katherine A. Martin ◽  
Daniel G. Star ◽  
Jesús Díaz ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Elemental Selenium ◽  
Cleavage Reaction ◽  
Ring Strain

The dimeric macrocyclophosphazane [{P(μ-NtBu)}2(μ-NtBu)]2 ( 1) was reacted with elemental selenium. An unexpected C–N cleavage reaction occurred producing P4(μ-NtBu)3(μ-NH)3Se4 ( 2). The C–N bond cleavage is driven by the high steric ring strain present within the ring.

Computational studies on Ni-catalyzed amide C–N bond activation

2019 ◽  
Vol 55 (76) ◽  
pp. 11330-11341 ◽  
Author(s):  
Hongliang Wang ◽  
Shuo-Qing Zhang ◽  
Xin Hong
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Mechanistic Models ◽  
Computational Studies

This review summarizes the mechanistic models of Ni-catalyzed amide C–N bond cleavage and discusses their applications in related transformations.

On the role of the surface oxygen species during A–H (A = C, N, O) bond activation: a density functional theory study

2015 ◽  
Vol 51 (13) ◽  
pp. 2621-2624 ◽  
Author(s):  
Jong Suk Yoo ◽  
Tuhin S. Khan ◽  
Frank Abild-Pedersen ◽  
Jens K. Nørskov ◽  
Felix Studt
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Oxygen Species ◽  
Final States ◽  
Surface Oxygen ◽  
Density Functional Theory Study ◽  
Reaction Energy ◽  
Functional Theory

During A–H (A = C, N, O) bond cleavage on O* or OH* pre-covered (111) surfaces, the oxygen species play the role of modifying the reaction energy by changing the species involved in the initial and final states of the reaction.

scholarly journals Heterolytic bond activation at gold: evidence for gold(iii) H–B, H–Si complexes, H–H and H–C cleavage

2019 ◽  
Vol 10 (9) ◽  
pp. 2633-2642 ◽  
Author(s):  
Luca Rocchigiani ◽  
Peter H. M. Budzelaar ◽  
Manfred Bochmann
Keyword(s):  
Dft Calculations ◽  
Bond Activation ◽  
Bond Cleavage

Gold(iii) forms spectroscopically detectable H–B and H–Si σ-complexes; experiments and DFT calculations demonstrate heterolytic H–Si, H–H and H–C bond cleavage.

Palladium-catalyzed C(carbonyl)–C bond cleavage of amides: a facile access to phenylcarbamate derivatives with alcohols

2018 ◽  
Vol 54 (62) ◽  
pp. 8606-8609 ◽  
Author(s):  
Xufei Yan ◽  
Huihui Sun ◽  
Haifeng Xiang ◽  
Da-Gang Yu ◽  
Daibing Luo ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Palladium Catalyzed ◽  
Sulfur Containing

A sulfur-containing auxiliary enabled palladium-catalyzed C(carbonyl)–C bond activation of amides was reported to form phenylcarbamate derivatives with alcohols.

Carbonfluorine bond activation by iron(I). CF bond cleavage induced by addition of phosphines or thiols to a perfluorovinyldiiron complex

1997 ◽  
Vol 533 (1-2) ◽  
pp. 177-185 ◽  
Author(s):  
René Rumin ◽  
Karine Guennou ◽  
Roger Pichon ◽  
François Y. Pétillon ◽  
Kenneth W. Muir ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage
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