7610-08-4Relevant academic research and scientific papers
Electrophilic substitution with allylic rearrangement (SE′) stereochemistry of trifluoroacetolysis of some cyclohex-2-enylmetal compounds
Wickham, Geoffrey,Young, David,Kitching, William
, p. 1187 - 1195 (2008/10/08)
A range of (4-alkylcyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)silanes, (4-alkylcyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)germanes, and (4-alkyl-cyclohex-2-enyl)-, (5-alkylcyclohex-2-enyl)-, and (6-alkylcyclohex-2-enyl)stannanes were cleaved to the cycloalkene (and R3MX) with trifluoroacetic acid-d in various solvents. Complete allylic rearrangement (γ-attack) was observed, and the preferred direction of delivery of the electrophile (formally D+) to the γ-carbon of the allylic triad was determined by detailed 1H, 13C, and 2H NMR analyses of the derived dibromides of the various alkyl-substituted cyclohexenes or by direct 2H NMR analysis and comparisons with 2H-substituted alkylcyclohexenes of established relative configurations. A highly preferred γ-anti mode of acidolysis is established for all systems, except for the trans-4-tert-butylcyclohex-2-enyl derivatives, such exception being ascribed to steric impedance of electrophile approach, promoting syn attack. Thus, overall, highly γ-regioselective and anti-stereoselective substitutions (SE′) are observed.
PROTOLYSES OF (CH3)3SnM(CH3)3 (M = Sn, Ge, SI, C)
Cuthberston, Matthew J.,Hawker, Darryl W.,Wells, Peter R.
, p. 7 - 24 (2007/10/02)
Product and kinetic studies on the reactions of hydrogen chloride in methanol solution with the substrates (CH3)3SnM(CH3)3 (M = Sn; Ge and Si) show that both Sn-M and Sn-CH3 cleavage reactions occur, at similar rates, and are followed by other reactions g
