Cycloaddition reactions of unactivated olefins catalyzed by an organorhenium electron-transfer mediator

Journal of the American Chemical Society

Volumn 131, Issue 23, 2009, Pages 7968-7969

  Chong, Daesung ^a   Stewart, Michael ^a   Geiger, William E ^a  

^a UNIVERSITY OF VERMONT   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC AMOUNTS; CHAIN-MECHANISM; CIS-CYCLOOCTENE; CYCLIC OLEFINS; CYCLIZATION REACTIONS; CYCLIZED PRODUCTS; CYCLOADDITION PRODUCTS; CYCLOADDITION REACTION; DIASTEREOMERIC; ELECTROCHEMICAL CONVERSION; ELECTROCHEMICAL PROCESS; ELECTROGENERATION; ELECTRON-TRANSFER; FERROCENE; ONE-ELECTRON OXIDATION; PHOTOCHEMICAL PROCESS; UNACTIVATED OLEFINS;

CYCLIZATION; CYCLOADDITION; IRON COMPOUNDS; MECHANISMS;

OLEFINS;

ALKENE; ORGANORHENIUM; RHENIUM; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; COUPLING FACTOR; CYCLOADDITION; ELECTROCHEMICAL ANALYSIS; ELECTRON TRANSPORT; MEDIATOR; PHOTOLYSIS; SYNTHESIS;

EID: 67650546953     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9032296     Document Type: Article

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27. The rate constant was measured from steady-state voltammograms using the treatment in Denuault, G.; Pletcher, D. J. Electroanal. Chem. 1991, 305, 131. Increases in the cyclic voltammetry anodic peak currents were also seen (see Supporting Information Figure S1).
28. 2 under nitrogen; electrolyze at 293 K for 15 min; add 30 mL of hexanes to precipitate supporting electrolyte; filter, evaporate, extract, and elute with hexane through activated alumina, affording 43 mg of an oil shown to be a mixture of 2 and its diastereomers.
29. Saturn 2100T with CP8944 column, methanol chemical ionization.
30. 7a but the original complex 1 may be regenerated by cathodic reduction of those side products.
31. 1/2 = 1.1 V in this medium), it lacks a metal center capable of expanding its coordination sphere. Compared to the Re-catalyzed process, the aminium-catalyzed reaction proceeds at a slower rate and gives greater product diversity. Detailed comparisons are under investigation.
32. The cyclized radical cation formed in eq 2 is a stronger oxidant than the radical cation of the olefin substrate. See ref 1a, pp 163-165.