Solvent Dynamics Regulated Electron Transfer in S2-Excited Sb and Ge Tetraphenylporphyrins with an Electron Donor Substituent at the Meso-Position

2014 ◽  
Vol 118 (22) ◽  
pp. 3926-3933 ◽  
Author(s):  
Mamoru Fujitsuka ◽  
Tsutomu Shiragami ◽  
Dae Won Cho ◽  
Sachiko Tojo ◽  
Masahide Yasuda ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Donor ◽  
Solvent Dynamics ◽  
Meso Position ◽  
Donor Substituent ◽  
Electron Donor Substituent

Gold-Catalyzed Partial Hydrogenation of Activated Alkynes Mediated by Triphenylphosphine

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2379-2386
Author(s):  
Susana Porcel ◽  
Ana Patricia Cocoletzi-Xochitiotzi ◽  
Miguel Hernández-Hernández ◽  
Ignacio Medina-Mercado ◽  
Williams de Jesús Jiménez-Martínez ◽  
...  
Keyword(s):  
Electron Donor ◽  
Cooperative Effect ◽  
Partial Hydrogenation ◽  
Aryl Ring ◽  
Activated Alkynes ◽  
Donor Substituent ◽  
Electron Donor Substituent

Gold(I) can exhibit a cooperative effect with triphenylphosphine, accelerating the triphenylphosphine-mediated partial hydrogenation of activated alkynes. In this protocol, 3-arylpropiolates are selectively reduced to the Z-isomer when the aryl ring bears an electron-donor substituent, whereas 3-arylpropynones are reduced to the E-isomers.

Recent Advances in the Chemistry of Doubly Activated Cyclopropanes: Synthesis and Reactivity

2019 ◽  
Vol 23 (3) ◽  
pp. 276-312 ◽  
Author(s):  
Purushothaman Gopinath ◽  
Srinivasan Chandrasekaran
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Electron Donor ◽  
Ring Opening ◽  
Dipolar Cycloaddition ◽  
Recent Advances ◽  
Donor Acceptor ◽  
Synthesis Reactions ◽  
Donor Substituent ◽  
Electron Donor Substituent

Diactivated cyclopropanes containing two geminal electron withdrawing groups, commonly called as ‘Doubly Activated Cyclopropanes’ are useful synthons for the synthesis of many interesting natural products and functionalized molecules. These geminal electron withdrawing groups (EWG’s) facilitate the regioselective ring opening of cyclopropanes by polarizing the C-C bond adjacent to it. This polarization also allows them to undergo 1,3 dipolar cycloaddition reactions when substituted with a suitable electron donor substituent at the adjacent carbon (donor-acceptor cyclopropanes) in the presence of suitable dipolarophiles. In this review, we discuss the recent advances in the chemistry of doubly activated cyclopropanes: their synthesis, reactions and applications in total synthesis.

scholarly journals Synthesis of an elusive, stable 2-azaallyl radical guided by electrochemical and reactivity studies of 2-azaallyl anions

2021 ◽  
Author(s):  
Grace B. Panetti ◽  
Patrick J. Carroll ◽  
Michael R. Gau ◽  
Brian C. Manor ◽  
Eric J. Schelter ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Donor ◽  
Transfer Characteristics

The super electron donor (SED) capabilities of 2-azaallyl anions has recently been discovered and applied to diverse reactivity; their structures and electron transfer characteristics are reported herein.

Volumes of activation for electrode processes of various charge-types in nonaqueous solvents

2001 ◽  
Vol 79 (12) ◽  
pp. 1864-1869 ◽  
Author(s):  
Mitsuru Matsumoto ◽  
Delanie Lamprecht ◽  
Michael R North ◽  
Thomas W Swaddle
Keyword(s):  
Electron Transfer ◽  
Reaction Rate ◽  
Electrode Reaction ◽  
State Theory ◽  
Exchange Reactions ◽  
Pt Electrode ◽  
Electrode Processes ◽  
Solvent Dynamics ◽  
The Mean ◽  
Dynamical Control

Volumes of activation (ΔV‡el) are reported for electron transfer at a Pt electrode of Mn(CN-cyclo-C6H11)62+/+ in acetonitrile, acetone, methanol, and propylene carbonate, and of Fe(phen)33+/2+ in acetonitrile. In all cases, ΔV‡el is markedly positive, whereas for the homogeneous self-exchange reactions of these couples in the same solvents the corresponding parameter is known to be strongly negative. The rate constants for the electrode reactions correlate loosely with the mean reactant diffusion coefficients (i.e., with solvent fluidity) and the ΔV‡el values with the volumes of activation for diffusion (i.e., for viscous flow), consistent with solvent dynamical control of the electrode reaction rate in organic solvents. A detailed analysis of ΔV‡el values of the kind presented for a couple with an uncharged member (Zhou and Swaddle, Can. J. Chem. 79, 841 (2001)) fails, however, either because of ion-pairing effects with these more highly charged couples or because of breakdown of transition-state theory in predicting the contribution of the activational barrier. Attempts to measure ΔV‡el for the oxidation of the uncharged molecule ferrocene at various electrodes in acetonitrile were unsuccessful, although ΔV‡el was again seen to be clearly positive.Key words: electrode kinetics, volumes of activation, nonaqueous electron transfer, solvent dynamics.

scholarly journals Electron donor-free photoredox catalysis via an electron transfer cascade by cooperative organic photocatalysts

2018 ◽  
Vol 8 (14) ◽  
pp. 3539-3547 ◽  
Author(s):  
Lei Wang ◽  
Irina Rörich ◽  
Charusheela Ramanan ◽  
Paul W. M. Blom ◽  
Wei Huang ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electron Donor ◽  
Photoredox Catalysis

Electron transfer cascade in cooperative organic photocatalysts can prevent the use of sacrificial reagent for photoredox catalysis.

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