Mechanistic Insights into C(sp
            2
            )−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes

The masked Ti(II) synthon (Ketguan)(η6-ImDippN)Ti (1) oxidatively adds across thiophene to give ring-opened (Ketguan)(ImDippN)Ti[κ2-S(CH)3CH] (2). Complex 2 is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate 1 – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from 2. Finally, pressurizing solutions of 2 with H2 (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (Ketguan)(ImDippN)Ti(S) (3) and butane.

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S(IV)–Mediated Unsymmetrical Heterocycle Cross-Couplings

10.26434/chemrxiv.11307710 ◽

2019 ◽

Author(s):

Min Zhou ◽

Jet Tsien ◽

Tian Qin

Keyword(s):

Cross Coupling ◽

Reductive Elimination ◽

Facile Synthesis ◽

Trigonal Bipyramidal

Herein we report a sulfur (IV) mediated cross-coupling for facile synthesis of heteroaromatic substrates. Addition of heteroaryl nucleophiles onto a simple, readily-accessible alkyl sulfinyl (IV) chloride allows formation of a trigonal bipyramidal sulfurane intermediate. Reductive elimination therefrom provides bis-heteroaryl products in a practical and efficient fashion.

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Carbon-Heteroatom Cross-Coupling via an Electronically Excited Nickel (II) Complex

10.26434/chemrxiv.9736049.v1 ◽

2019 ◽

Author(s):

Randolph Escobar ◽

Jeffrey Johannes

Keyword(s):

Energy Transfer ◽

Functional Groups ◽

Cross Coupling ◽

Reductive Elimination ◽

Aryl Halides ◽

Coupling Reactions ◽

General Methodology ◽

Cross Coupling Reactions ◽

Electronically Excited ◽

Energy Transfer Pathway

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>

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Reductive elimination reaction of β-nitrosulfones via one electron transfer process. A new synthetic method for the preparation ofα,β-unsaturated nitriles and esters

Tetrahedron Letters ◽

10.1016/s0040-4039(01)85389-2 ◽

1978 ◽

Vol 19 (8) ◽

pp. 763-764 ◽

Cited By ~ 11

Author(s):

Noboru Ono ◽

Rui Tamura ◽

Jun-ichi Hayami ◽

Aritsune Kaji

Keyword(s):

Electron Transfer ◽

Transfer Process ◽

Reductive Elimination ◽

Synthetic Method ◽

Elimination Reaction ◽

Electron Transfer Process

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Force-modulated reductive elimination from platinum(ii) diaryl complexes

Chemical Science ◽

10.1039/d1sc03182a ◽

2021 ◽

Author(s):

Yichen Yu ◽

Chenxu Wang ◽

Liqi Wang ◽

Cai-Li Sun ◽

Roman Boulatov ◽

...

Keyword(s):

Transition State ◽

Reductive Elimination ◽

Mechanical Force ◽

Elimination Reactions

The influence of mechanical force on the rates of model reductive elimination reactions depends on the structure of the force-transducing ligand and provides a measure of geometry changes upon reaching the transition state.

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