3948-42-3Relevant academic research and scientific papers
Iridium-catalyzed addition of acid chlorides to terminal alkynes
Iwai, Tomohiro,Fujihara, Tetsuaki,Terao, Jun,Tsuji, Yasushi
supporting information; experimental part, p. 6668 - 6669 (2009/10/30)
(Chemical Equation Presented) An iridium N-heterocyclic carbene (NHC) complex, IrCl(cod)(IPr), successfully catalyzed an addition of common aromatic acid chlorides to terminal alkynes to afford (Z)-β-chloro-α,β- unsaturated ketones regio- and stereoselectively. When the NHC ligand (IPr) was changed to a phosphine (RuPhos), the addition occurred with decarbonylation to give the corresponding (Z)-vinyl chlorides. Furthermore, the former reaction using IrCl(cod)(IPr) can be applied to the catalytic synthesis of 2,5-disubstituted furans.
An easy access to trisubstituted vinyl chlorides and improved synthesis of chloro/bromostilbenes
Muthiah,Kumar, K. Praveen,Kumaraswamy, Sudha,Kumara Swamy
, p. 14315 - 14326 (2007/10/03)
The α-chlorophosphonates (OCH2CMe2CH2O)P(O)CHCl-C6H4-4-R [R=H (4), Me (5), OMe (6)], which are now readily accessible, react with ketones R'C(O)R' in the presence of NaH (without recourse to the more expensive t- BuLi) to afford trisubstituted vinyl halides R'C(R')=CCl(C6H4-4-R) in good yields. The corresponding α-bromophosphonates [R=H (7), Me (8)] failed to react with ketones and gave the symmetrical acetylenes 4-R-C6H4-C=C- C6H44-R as isolable products in low yield. We have found that K2CO3 in refluxing xylene is a good base for the synthesis of chlorostilbenes; using this base the bromostilbenes ArCH=CBr(C6H44-R) can be prepared in significantly higher yields than by using NaH. The stereochemistry of two of the trisubstituted vinyl chlorides is unambiguously proven by X-ray structure determination. Thus for (Cl)PhC=CPh(Me), the isomer with the upfield NMR shift for the CH3 protons and for (Cl)PhC=C(Ph)(C6H4-4-Me), the isomer with the downfield NMR shift for the -C6H4-4-CH3 protons have Z stereochemistry.
A convenient route to aryl substituted chloro and bromo olefins
Kumaraswamy, Sudha,Kumara Swamy
, p. 2183 - 2184 (2007/10/03)
A wide range of aryl substituted chloro and bromo olefins has been prepared by treating α-chloro and α-bromophosphonates derived from 1-hydrido-5,5-dimethyl-1,3,2-dioxaphosphorinane with sodium hydride in THF at 0°C followed by an aldehyde.
Rhodium-catalyzed reaction of aroyl chlorides with alkynes
Kokubo, Ken,Matsumasa, Kenji,Miura, Masahiro,Nomura, Masakatsu
, p. 6941 - 6946 (2007/10/03)
Aroyl chlorides react with terminal alkynes accompanied by decarbonylation in the presence of a catalytic amount of [RhCl(cod)]2 and PPh3 to give the corresponding vinyl chloride derivatives regioand stereoselectively in good yields.
