1245947-04-9Relevant articles and documents
Gold-Catalyzed Highly Chemo- and Regioselective C-H Bond Functionalization of Phenols with Haloalkynes
Adak, Tapas,Schulmeister, Jürgen,Dietl, Martin C.,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 3867 - 3876 (2019)
A highly chemo- and stereoselective addition of unprotected phenols to haloalkynes was developed. A ligand and counterion controlled process enabled the highly site-selective and chemoselective C-H bond functionalization of phenol derivatives with haloalkynes in moderate to excellent yield at room temperature. The simple availability of the starting materials in combination with the preferred para-C-H functionalization over a competing O-H insertion makes this an attractive protocol. The stereoselectivity of the products depends on the choice of the catalyst. From a synthetic prospective, this method offers an efficient route towards vinyl chlorides, which are valuable precursors for the synthesis of pharmaceutical drugs.
Palladium-catalyzed modular assembly of electron-rich alkenes, dienes, trienes, and enynes from (E)-1,2-dichlorovinyl phenyl ether
Geary, Laina M.,Hultin, Philip G.
experimental part, p. 6354 - 6371 (2010/12/19)
We have devised a modular construction of electron-rich alkene derivatives from trichloroethylene (TCE). The three C-l bonds of TCE have sufficiently different reactivities that they can be sequentially and selectively functionalized. Following the substitution of one chlorine by phenol to generate (E)-1,2-dichlorovinyl ether, the C1-Cl group next participates in palladium-catalyzed cross-coupling reactions with a variety of organometallic reagents. Subsequently, the C2-Cl group can engage in cross-couplings, while the C2-H may be deprotonated and quenched with an electrophile. Thus, isomerically pure tri- and tetrasubstituted electron-rich alkenes may be accessed in as few as two steps from simple and inexpensive starting materials. This method is ideally suited for diversity-oriented synthesis of highly conjugated molecules of interest as chromophores or as potential molecular electronics. It also gives access to diverse building blocks for further synthetic elaboration into high-value compounds.
