scholarly journals Consecutive O−S/N−S Bond Cleavage in Au‐Catalyzed Rearrangement Reactions of Alkynyl N ‐Sulfinylimines

2021 ◽  
Author(s):  
Hiroki Tashiro ◽  
Masahiro Terada ◽  
Itaru Nakamura
Keyword(s):  
Bond Cleavage ◽  
Rearrangement Reactions

scholarly journals Photoinduced transition-metal- and external-photosensitizer-free intramolecular aryl rearrangement via C(Ar)–O bond cleavage

2020 ◽  
Vol 11 (22) ◽  
pp. 5740-5744 ◽  
Author(s):  
Qian Dou ◽  
Chao-Jun Li ◽  
Huiying Zeng
Keyword(s):  
Transition Metal ◽  
Bond Cleavage ◽  
Rearrangement Reactions

“We report a protocol for photoinduced transition-metal- and external-photocatalyst-free intramolecular heteroaryl/aryl rearrangement reactions of 2-heteroaryl/aryloxybenzaldehydes. The protocol was compatible with a variety of functionalities.

scholarly journals Rearrangements of organic peroxides and related processes

2016 ◽  
Vol 12 ◽  
pp. 1647-1748 ◽  
Author(s):  
Ivan A Yaremenko ◽  
Vera A Vil’ ◽  
Dmitry V Demchuk ◽  
Alexander O Terent’ev
Keyword(s):  
Molecular Weight ◽  
Bond Cleavage ◽  
Organic Peroxides ◽  
Rearrangement Reactions ◽  
Natural And Synthetic

This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

Tuneable access to isoquinolines via a transition-metal-free C(sp3)–C(sp3) bond cleavage rearrangement reaction

2019 ◽  
Vol 6 (14) ◽  
pp. 2430-2434 ◽  
Author(s):  
Jian Wang ◽  
Panyuan Cai ◽  
Yimiao He ◽  
Yuan Liu ◽  
Ling Zhong ◽  
...  
Keyword(s):  
Transition Metal ◽  
Bond Cleavage ◽  
Metal Free ◽  
Rearrangement Reaction ◽  
Rearrangement Reactions

A novel divergent synthesis of multi-substituted isoquinolines via C(sp3)–C(sp3) bond cleavage rearrangement reactions was realized.

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.

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

Oxygen-Oxygen Bond Cleavage and Formation in Co(II) Mediated Stoichiometric O2 Reduction via the Potential Intermediacy of a Co(IV) Oxyl Radical

2018 ◽  
Author(s):  
Lucie Nurdin ◽  
Denis M. Spasyuk ◽  
Laura Fairburn ◽  
Warren Piers ◽  
Laurent Maron
Keyword(s):  
Bond Cleavage ◽  
Peroxo Complex ◽  
Oxygen Oxygen ◽  
O2 Reduction ◽  
Oxygen Bond ◽  
Pentadentate Ligand

Diprotonation of a remarkably stable, toluene soluble cobalt peroxo complex supported by a neutral, dianionic pentadentate ligand leads to facile O-O bond cleavage and production of a highly reactive Co(IV) oxyl cation intermediate that dimerizes and releases O<sub>2</sub>. These processes are relevant to both O<sub>2</sub> reduction and O<sub>2</sub> evolution and the mechanism was probed in detail both experimentally and computationally.

Sign in / Sign up

Export Citation Format

Share Document