Chemoselective reduction of the phosphoryl bond of O-alkyl phosphinates and related compounds: an apparently impossible transformation

2015 ◽  
Vol 51 (92) ◽  
pp. 16561-16564 ◽  
Author(s):  
Niall P. Kenny ◽  
Kamalraj V. Rajendran ◽  
Declan G. Gilheany
Keyword(s):  
Bond Cleavage ◽  
Related Compounds

A method is reported for the phosphoryl bond cleavage of O-alkyl phosphinates, phosphinothioates and certain phosphonamidates to furnish the corresponding P(iii) borane adducts.

Rhodium-Catalyzed Mono- and Divinylation of 1-Phenylpyrazoles and Related Compounds via Regioselective C−H Bond Cleavage

2009 ◽  
Vol 74 (18) ◽  
pp. 7094-7099 ◽  
Author(s):  
Nobuyoshi Umeda ◽  
Koji Hirano ◽  
Tetsuya Satoh ◽  
Masahiro Miura
Keyword(s):  
Bond Cleavage ◽  
Related Compounds

Nucleic acid related compounds. 78. Stereocontrolled syntheses of 6′(E and Z)-halovinyl analogues from uridine-derived vinylsulfones via vinyltin intermediates

1993 ◽  
Vol 71 (2) ◽  
pp. 192-198 ◽  
Author(s):  
Stanislaw F. Wnuk ◽  
Morris J. Robins
Keyword(s):  
Nucleic Acid ◽  
Trifluoroacetic Acid ◽  
Bond Cleavage ◽  
Lead Tetraacetate ◽  
Acetylenic Derivative ◽  
Vinyl Derivative ◽  
High Yields ◽  
Related Compounds

Treatment of the 6′(E)-tosylvinyl homonucleoside 1a with Bu3SnH/AIBN/toluene/Δ gave separable mixtures of 6′-vinylstannanes 2a(E/Z) in high yields. Stereospecific halodestannylations with N-iodosuccinimide, bromine, and N-bromosuccinimide proceeded smoothly to give the 6′(E or Z)-iodo(and bromo) vinyl compounds with retention of configuration. Chlorine or iodobenzene dichloride effected moderately stereoselective chlorodestannylation. Treatment of 2a with NH4F/MeOH/Δ resulted in carbon–tin bond cleavage to give the free vinyl derivative 4a. Aqueous trifluoroacetic acid effected concomitant protiodestannylation and deprotection of 2a to give 4b. Treatment of 2a(E) with lead tetraacetate/acetonitrile and deprotection afforded acetylenic derivative 3b.

Rhodium-catalyzed regioselective arylation of phenylazoles and related compounds with arylboron reagents via C–H bond cleavage

2008 ◽  
Vol 693 (14) ◽  
pp. 2438-2442 ◽  
Author(s):  
Sawako Miyamura ◽  
Hayato Tsurugi ◽  
Tetsuya Satoh ◽  
Masahiro Miura
Keyword(s):  
Bond Cleavage ◽  
Related Compounds

scholarly journals Exploring the effects of quantum decoherence on the excited-state dynamics of molecular systems

2021 ◽  
Vol 140 (4) ◽  
Author(s):  
Eric R. Heller ◽  
Jan-Ole Joswig ◽  
Gotthard Seifert
Keyword(s):  
Excited State ◽  
Potential Energy ◽  
Density Functional ◽  
Bond Cleavage ◽  
Minimum Energy ◽  
Quantum Decoherence ◽  
Ensemble Averaging ◽  
Excited State Dynamics ◽  
Complete Active Space ◽  
Related Compounds

AbstractFewest-switches surface hopping (FSSH) is employed in order to investigate the nonadiabatic excited-state dynamics of thiophene and related compounds and hence to establish a connection between the electronic system, the critical points in configuration space and the deactivation dynamics. The potential-energy surfaces of the studied molecules were calculated with complete active space self-consistent field and time-dependent density-functional theory. They are analyzed thoroughly to locate and optimize minimum-energy conical intersections, which are essential to the dynamics of the system. The influence of decoherence on the dynamics is examined by employing different decoherence schemes. We find that irrespective of the employed decoherence algorithm, the population dynamics of thiophene give results which are sound with the expectations grounded on the analysis of the potential-energy surface. A more detailed look at single trajectories as well as on the excited-state lifetimes, however, reveals a substantial dependence on how decoherence is accounted for. In order to connect these findings, we describe how ensemble averaging cures some of the overcoherence problems of uncorrected FSSH. Eventually, we identify carbon–sulfur bond cleavage as a common feature accompanying electronic transitions between different states in the simulations of all thiophene-related compounds studied in this work, which is of interest due to their relevance in organic photovoltaics.

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