77527-92-5Relevant academic research and scientific papers
Cathodic Addition of Benzylidyne Trichloride to Ketones and Aldehydes
Steiniger, Michael,Schaefer, Hans J.
, p. 125 - 132 (1988)
Ketones are converted to homologated enones 7a-g in good yields by cathodic addition of benzylidyne trichloride (1d).As intermediates α-Chlorooxiranes 6 are assumed, which rearrange via α-keto carbenium ions 9 to enones.The intermediacy of 9 is supported by the addition of 1d to norcamphor, where the products indicate equilibrating norbornyl cations as intermediates. α,β-Unsaturated ketones lead depending on steric shielding of the double bond to the cyclopropane 23 as 1,4-adduct or the enone 26 as 1,2-adduct.With aldehydes and 1d, α-chloro or βhydroxy ketones, the conversion products of 2-chlorooxiranes, are obtained.
Easy and General Synthesis of Unsymmetrical α-Halogeno Ketones
Barluenga, Jose,Llavona, Lujan,Yus, Miguel,Concellon, Jose M.
, p. 2890 (2007/10/02)
The reaction of carboxylic acid esters 1 with in situ generated bromohalomethyllithium (1:2 molar ratio) at -78 deg C followed by reaction with lithium dialkylcuprate (1:1 molar ratio) at 0 deg C, leads, after hydrolysis, to the corresponding α-chloro or α-bromo ketones 3.
Proprietes nucleophiles des carbenoides monohalogenes non fonctionnels
Villieras, J.,Kirschleger, B.,Tarhouni, R.,Rambaud, M.
, p. 470 - 478 (2007/10/02)
The coupling of non functionalised monohalocarbenoids R1-CXLi-R2 1 (R1 = alkyl, H ; R2 = H, CH3) with carbonyl compounds at -115 degree leads to the formation of lithium salts of halohydrins which readily give epoxides (via lithium halide elimination) at -95 degree in the presence of lithium bromide.The regiospecific synthesis of α-haloketones and α-haloaldehydes can be achieved by acylation of 1 with esters.A total lack of reactivity of 1 towards powerful alkylating electrophiles has been observed showing that they are not nucleophilic organometallics.The reactivity with carbonyl compounds seems to be promoted by the carbonyl-lithium (from the carbenoid) complexation.A correlation between nucleophilic/electrophilic properties of carbenoids (mono-, di- and trihalo-) and their assigned structure (metallocarbenium halides) is discussed.
