C–F bond activation by iridium(I). A unique process involving P–C bond cleavage, P–F bond formation and net retention of oxidation state

1991 ◽  
Vol 0 (4) ◽  
pp. 258-259 ◽  
Author(s):  
Ofer Blum ◽  
Felix Frolow ◽  
David Milstein
Keyword(s):  
Oxidation State ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation

Palladium-catalyzed C–S bond activation and functionalization of 3-sulfenylindoles and related electron-rich heteroarenes

2017 ◽  
Vol 4 (8) ◽  
pp. 1590-1594 ◽  
Author(s):  
Jianxiao Li ◽  
Yanni An ◽  
Jiawei Li ◽  
Shaorong Yang ◽  
Wanqing Wu ◽  
...  
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Palladium Catalyzed

A novel palladium-catalyzed approach for constructing functionalized heteroarenes via C–S bond cleavage and C–C bond formation has been demonstrated.

scholarly journals Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)3

2015 ◽  
Vol 6 (7) ◽  
pp. 4255-4260 ◽  
Author(s):  
A. L. Raza ◽  
T. Braun
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Cleavage Reaction ◽  
Bond Cleavage Reaction ◽  
Consecutive Reactions ◽  
Silyl Complex

C–F activation reactions for a silyl complex gave fluorosilane and Rh pyridyl complexes. In consecutive reactions, the fluorosilane can act as a fluoride source and a regeneration of the C–F bond occurs by Si–F bond cleavage. This sets back the C–F bond cleavage reaction with consequences for the overall chemoselectivity of the activation reactions.

scholarly journals Aluminium-mediated aromatic C–F bond activation: regioswitchable construction of benzene-fused triphenylene frameworks

2016 ◽  
Vol 52 (88) ◽  
pp. 12948-12951 ◽  
Author(s):  
Naoto Suzuki ◽  
Takeshi Fujita ◽  
Konstantin Yu. Amsharov ◽  
Junji Ichikawa
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Selective Synthesis

Aluminium-mediated selective synthesis of benzo[f]tetraphenes or benzo[g]chrysenes was achieved via aromatic C–F bond cleavage and regioselective C–C bond formation.

Pyridine-mediated B-B Bond Activation of (RO)2B-B(OR)2 for Generating Borylpyridine Anions and Pyridine-stabilized Boryl Radicals as Useful Boryl Reagents in Organic Synthesis

Synthesis ◽  
2021 ◽  
Author(s):  
Luis Carlos Misal Castro ◽  
Ibrahim Sultan ◽  
Hayato Tsurugi ◽  
Kazushi Mashima
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Pyridine Derivatives ◽  
Organic Transformations ◽  
Lewis Bases ◽  
Metal Free ◽  
Synthetic Utility

Significant developments have been achieved in recent years toward the utilization of (RO)2B-B(OR)2 for exploring transition metal-free organic transformations in organic synthesis. Among the various combinations of Lewis bases with diborons developed so far, pyridine-derivatives are simple, commercially available, and cheap compounds to expand the synthetic utility of diborons by generating borylpyridine anions and pyridine-stabilized boryl radicals via the B-B bond cleavage. These borylpyridine species mediate a series of transformations in both a catalytic and stoichiometric manner for C-X activation (X = Halogen, CO2H, NR2) and concomitant C-borylation, hydroboration, C-C bond formation, and reduction reactions.

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.

Imine as a Linchpin Approach for Distal C(sp2)–H Functionalization

2020 ◽  
Author(s):  
Sukdev Bag ◽  
Sadhan Jana ◽  
Sukumar Pradhan ◽  
Suman Bhowmick ◽  
Nupur Goswami ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Bond Activation ◽  
Bond Formation ◽  
Ancillary Ligand ◽  
Significant Challenge ◽  
Site Selectivity ◽  
Directing Group ◽  
Covalently Linked ◽  
Complex Organic ◽  
Post Functionalization

<p>Despite the widespread applications of C–H functionalization, controlling site selectivity remains a significant challenge. Covalently attached directing group (DG) served as an ancillary ligand to ensure proximal <i>ortho</i>-, distal <i>meta</i>- and <i>para</i>-C-H functionalization over the last two decades. These covalently linked DGs necessitate two extra steps for a single C–H functionalization: introduction of DG prior to C–H activation and removal of DG post-functionalization. We introduce here a transient directing group for distal C(<i>sp<sup>2</sup></i>)-H functionalization <i>via</i> reversible imine formation. By overruling facile proximal C-H bond activation by imine-<i>N</i> atom, a suitably designed pyrimidine-based transient directing group (TDG) successfully delivered selective distal C-C bond formation. Application of this transient directing group strategy for streamlining the synthesis of complex organic molecules without any necessary pre-functionalization at the distal position has been explored.</p>

Carbon Dioxide-Mediated C(sp2)–H Arylation of Primary and Secondary Benzylamines

2018 ◽  
Author(s):  
Mohit Kapoor ◽  
Pratibha Chand-Thakuri ◽  
Michael Young
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Carbon Bond ◽  
Chelate Effect ◽  
Free Amine ◽  
Carbon Carbon Bond ◽  
New Strategy ◽  
Metal Catalyzed

Carbon-carbon bond formation by transition metal-catalyzed C–H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of <i>ortho</i>-arylbenzylamines, however, effective <i>ortho</i>-C–C bond formation from C–H bond activation of free primary and secondary benzylamines using Pd<sup>II</sup> remains an outstanding challenge. Presented herein is a new strategy for constructing <i>ortho</i>-arylated primary and secondary benzylamines mediated by carbon dioxide (CO<sub>2</sub>). The use of CO<sub>2</sub> is critical to allowing this transformation to proceed under milder conditions than previously reported, and that are necessary to furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, a chelate effect is demonstrated to facilitate selective monoarylation.

Peptide Modifications: Versatile Tools in Peptide and Natural Product Syntheses

Synlett ◽  
2019 ◽  
Vol 30 (11) ◽  
pp. 1289-1302 ◽  
Author(s):  
Phil Servatius ◽  
Lukas Junk ◽  
Uli Kazmaier
Keyword(s):  
Amino Acids ◽  
Natural Product ◽  
Bond Activation ◽  
Bond Formation ◽  
Side Chain ◽  
Peptide Backbone ◽  
Claisen Rearrangements ◽  
The Past ◽  
Allylic Alkylations ◽  
Peptide Modifications

Peptide modifications via C–C bond formation have emerged as valuable tools for the preparation and alteration of non-proteinogenic amino acids and the corresponding peptides. Modification of glycine subunits in peptides allows for the incorporation of unusual side chains, often in a highly stereoselective manner, orchestrated by the chiral peptide backbone. Moreover, modifications of peptides are not limited to the peptidic backbone. Many side-chain modifications, not only by variation of existing functional groups, but also by C–H functionalization, have been developed over the past decade. This account highlights the synthetic contributions made by our group and others to the field of peptide modifications and their application in natural product syntheses.1 Introduction2 Peptide Backbone Modifications via Peptide Enolates2.1 Chelate Enolate Claisen Rearrangements2.2 Allylic Alkylations2.3 Miscellaneous Modifications3 Side-Chain Modifications3.1 C–H Activation3.1.1 Functionalization via Csp3–H Bond Activation3.2.2 Functionalization via Csp2–H Bond Activation3.2 On Peptide Tryptophan Syntheses4 Conclusion

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.

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