68857-86-3Relevant academic research and scientific papers
Palladium-Catalyzed Synthesis of α-Methyl Ketones from Allylic Alcohols and Methanol
Biswal, Priyabrata,Samser, Shaikh,Meher, Sushanta Kumar,Chandrasekhar, Vadapalli,Venkatasubbaiah, Krishnan
, p. 413 - 419 (2021/11/01)
One-pot synthesis of α-methyl ketones starting from 1,3-diaryl propenols or 1-aryl propenols and methanol as a C1 source is demonstrated. This one-pot isomerization-methylation is catalyzed by commercially available Pd(OAc)2 with H2O as the only by-product. Mechanistic studies and deuterium labelling experiments indicate the involvement of isomerization of allyl alcohol followed by methylation through a hydrogen-borrowing pathway in these isomerization-methylation reactions.
Rhodium-Catalyzed Direct Ortho C-H Arylation Using Ketone as Directing Group with Boron Reagent
Zhang, Bing,Wang, Huai-Wei,Kang, Yan-Shang,Zhang, Ping,Xu, Hua-Jin,Lu, Yi,Sun, Wei-Yin
supporting information, p. 5940 - 5943 (2017/11/10)
A general method for selective ortho C-H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.
Mechanisms of Elimination Reactions. 39. Steric and Electronic Effects on Stereochemistry in Eliminations from Primary Alkyltrimethylammonium Salts
Dohner, Brent R.,Saunders, William H. Jr.
, p. 245 - 247 (2007/10/02)
Percentages of syn elimination have been determined by high-field NMR on the products of elimination from R1R2CHCHDX.The results for X=OTs with t-BuO(-)/t-BuOH at 60 deg C were the following (R1, R2, percent syn): p-MeOC6H4, C6H5, 3.7; p-ClC6H4, C6H5, 29; p-ClC6H4, C6H5, 0 in EtO(-)/EtOH.For X=NMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercentH2O at 60 deg C, the results were as follows (R1, R2, percent syn): p-MeOC6H4, C6H5, 60; p-ClC6H4, C6H5, 72.For Ar(i-Pr)CHCHDNMe3(+) with OH(-) in 50 molpercent Me2SO-50 molpercent H2O at 80 deg C, the results were as follows (Ar, percent syn): m-ClC6H4, 78.6; p-ClC6H4, 69.5; C6H5, 59.6; p-EtC6H4, 58.3; p-t-BuC6H4, 60.5.Overall rates in this series were dissected into syn and anti rates, which fitted the Hammett equation to give ρsyn=3.69 +/- 0.20 and ρanti=3.02 +/- 0.22.This result supports the conclusion that syn elimination has a more carbanionic transition state than anti.The lower percent syn with X=OTs than with X=NMe3(+) is ascribed to the lesser steric requirements of OTs.
Novel acyl-polyalkylindan compounds and the use thereof as a base for perfume, as well as perfume compositions
-
, (2008/06/13)
Novel acyl-polyalkyl indan compounds and the use thereof as a base for perfume, as well as perfume compositions, perfumed materials and perfumed articles.
Acylation of aromatic substrates with ketenes. An example of vinyl oxocation reactivity.
Fountain, K.R.,Heinze, Pamela,Sherwood, Mark,Maddex, Dave,Gerhardt, Greg
, p. 1198 - 1205 (2007/10/02)
Acylations of aromatic substrates with ketenes involve the reactivity of species similar to vinyl cations.Resonance stabilization of ketene-aluminum chloride complexes seems to make these complexes less reactive than corresponding vinyl cations.The kinetic isotope effect of the reaction with dimethylketene and benzene is 1.06, compatible with vinylcation cases, but not with acylation with CH3COBF4 types of electrophiles.Substrate specificity was determined from k (toluene)/k (benzene) values.It was 47.2 for dimethylketene and 173.7 for diphenylketene.The diphenylketene-aluminum chloride complex could be isolated.
