285-58-5Relevant articles and documents
Formation of Cyclopropanes via Activation of (γ-Methoxy)alkyl Gold(I) Complexes with Lewis Acids
Kim, Nana,Widenhoefer, Ross A.
, p. 3160 - 3167 (2020/09/12)
Treatment of the gold 3-methoxy-3-phenylpropyl complex (P)AuCH2CH2CH(OMe)Ph [P = P(t-Bu)2o-biphenyl] with AlCl3 at -78 °C led to the immediate (≤5 min) formation of a 4:1 mixture of phenylcyclopropane and (1-methoxypropyl)benzene in 86 ± 5% combined yield. Lewis acid activation of the stereochemically pure isotopomer erythro-(P)AuCH2CHDCH(OMe)Ph led to the formation of cis-2-deuterio-1-phenylcyclopropane in 84 ± 5% yield as a single stereoisomer, which established that cyclopropanation occurred with inversion of the γ-stereocenter. Similarly, ionization of the stereochemically pure cyclohexyl gold complex cis-(P)AuCHCH2CH(OMe)CH2CH2CH2 at -78 °C formed bicyclo[3.1.0]hexane in 82% ± 5% yield, which validated a low energy pathway for cyclopropanation involving inversion of the α-stereocenter. Taken together, these observations are consistent with a mechanism for cyclopropane formation involving backside displacement of both the Cγleaving group and the Cα (L)Au+ fragment via a W-shaped transition state.
The diagnostic substrate bicyclohexane reveals a radical mechanism for bacterial cytochrome P450 in whole cells
Austin, Rachel N.,Deng, Dayi,Jiang, Yongying,Luddy, Kate,Van Beilen, Jan B.,Ortiz De Montellano, Paul R.,Groves, John T.
, p. 8192 - 8194 (2008/02/08)
(Figure Presented) On home ground: The reaction mechanisms of bacterial alkane-oxidizing cytochrome P450s were determined in their native environment using a novel diagnostic substrate probe, bicyclohexane, in whole cells and cell-free extracts (see picture). Purified P450cam also oxidizes bicyclohexane. Clear evidence for a substrate-based radical with a lifetime of 75-250 ps was obtained.
Preparation of Bicycloalkanes by Electrochemical Reduction of 1,3-Dibromocycloalkanes
Hoffmann, Joachim,Voss, Juergen
, p. 1415 - 1420 (2007/10/02)
Good yields of bicyclo pentane (17) and bicyclo-hexane(3) are obtained on electroreduction of the corresponding 1,3-dibromocycloalkanes.The results do not depend upon the stereochemistry of the starting material (14 vs. 15 or 11 vs. 12).Key Words: Electrochemical reduction / Bicycloalkanes / Cycloalkanes, 1,3-dibromo / Hunsdiecker reaction / 1,3-Cycloalkanedicarboxylic acids
Generation of a Carbenoid by Cyclization of 6-Chloro-5-hexen-1-yllithium
Dolbier, William R.,Chen, Yaxiong
, p. 1947 (2007/10/02)
Bicyclohexane and methylenecyclopentane, products deriving from an apparent carbenoid intermediate, have been observed in the intramolecular cyclization reaction of 6-chloro-5-hexen-1-yllithium.
