Mechanistic Study of the N-Formylation of Amines with Carbon Dioxide and Hydrosilanes
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The reaction or organo-lithium or cuprate derivs. towards the cyano group of 2-cyano-6-phenyloxazolopiperidine synthon I gives an imine which is reduced to a primary amine with a remarkable stereoselectivity. An application of this reaction to the synthesi ...
Ylides Ph3P+C-RR1 (R = H, Me; R1 = OMe, Cl, Me, Pr, Ph, CO2Me) underwent Wittig reaction with fluoroalkenals MeCR2:CFCHO (R2 = H, Me) to give 52-95% MeCR2:CFCH:CRR1. This reaction occurred at approx. the same rate, and gave nearly the same Z-E mixts., as t ...
HCl and HBr were easily abstracted from secondary and tertiary alkyl halides by KOH in tetraglyme, but primary alkyl halides yielded approx. equal amts. of elimination and substitution products (alkenes and alcs. and/or ethers). However, the addn. of catal ...
Cycloaddn. of ClFC.bul. to olefins RR1C:CHR2 (R = alkyl or substituted alkyl, e.g., Et, ClCH2, AcOCH2CH2CH2; R1 = H, Me, Et; R2 = H, Me) gave 1-chloro-1-fluorocyclopropanes; these were acetolyzed to RR1C:CFCHR2OAc, which were hydrolyzed to RR1C:CFCHR2OH. T ...
Reaction of cis- and trans-PhCH:CHF with RLi (R = Bu, Me, Ph, or PhCH2) gave stereoselectively cis- and trans-PhCH:CHR, with retention of configuration by substitution and PhC.tplbond.CH by elimination reaction. The elimination reaction follows mainly the ...
Short-wavelength irradn. of Ph3P+C-Me2 gave C6H6 and a resinous compd. Long-wavelength irradn. of Ph3P+C-Me2 gave mainly Ph3P and Me2C:CMe2 with some Me2CHCHMe2, MeCH:CH2, and, with Me2CHCHMe2 as solvent, traces of (Me2CH)2CMe2 and Me2CHCHMeCH2CHMe2. the r ...
7-Halo-7-methylnorcaranes (I) and 7,7-dimethylnorcarane (II) are formed via replacement of halogen by Me during the reaction of cyclohexene (III) with carbenes (carbenoids) and MeLi. Thus, III is treated with CHClF2 or CCl2F2 and MeLi to give a mixt. of 7- ...
The reverse water gas shift reaction is considered to be a highly attractive catalytic route for CO2 recycling in a future sustainable economy. Copper-based catalysts are commonly used for this reaction due to their high activity and selectivity. However, ...