62640-56-6Relevant articles and documents
Synthesis of Highly Substituted Arenes via Cyclohexadiene-Alkene C-H Cross Coupling and Aromatization
Bhunia, Anup,Studer, Armido
, p. 1213 - 1217 (2018/02/14)
The development of a cross-coupling method for the regioselective β-alkenylation of 2,5-cyclohexadiene carboxylic acid derivatives to form ortho-alkenylarenes through in situ decarboxylation and aromatization is described. The carboxylic acid functionality is used as a traceless directing group for efficient and mild β-alkenylation. The modular sequence comprises a reductive Birch α-alkylation, ionic ?-alkylation followed by a Pd-catalyzed decarboxylative β-alkenylation with subsequent aromatization resulting in an overall three-fold ipso-para-ortho functionalization of readily accessed benzoic acid derivatives. Efficient synthesis of various alkyl-alkenylarenes under mild conditions in moderate to excellent yields is presented.
Unequivocal experimental evidence for a unified lithium salt-free wittig reaction mechanism for all phosphonium ylide types: Reactions with β-heteroatom-substituted aldehydes are consistently selective for cis-oxaphosphetane-derived products
Byrne, Peter A.,Gilheany, Declan G.
, p. 9225 - 9239 (2012/07/14)
The true course of the lithium salt-free Wittig reaction has long been a contentious issue in organic chemistry. Herein we report an experimental effect that is common to the Wittig reactions of all of the three major phosphonium ylide classes (non-stabilized, semi-stabilized, and stabilized): there is consistently increased selectivity for cis-oxaphosphetane and its derived products (Z-alkene and erythro-β-hydroxyphosphonium salt) in reactions involving aldehydes bearing heteroatom substituents in the β-position. The effect operates with both benzaldehydes and aliphatic aldehydes and is shown not to operate in the absence of the heteroatom substituent on the aldehyde. The discovery of an effect that is common to reactions of all ylide types strongly argues for the operation of a common mechanism in all Li salt-free Wittig reactions. In addition, the results are shown to be most easily explained by the [2+2] cycloaddition mechanism proposed by Vedejs and co-workers as supplemented by Aggarwal, Harvey, and co-workers, thus providing strong confirmatory evidence in support of that mechanism. Notably, a cooperative effect of ortho-substituents in the case of semi-stabilized ylides is confirmed and is accommodated by the cycloaddition mechanism. The effect is also shown to operate in reactions of triphenylphosphine-derived ylides and has previously been observed for reactions under aqueous conditions, thus for the first time providing evidence that kinetic control is in operation in both of these cases.
(E)-(2-Bromoethenyl)dibromoborane. A New Precursor for (E)-1,2-Disubstituted Ethenes
Hyuga, Satoshi,Chiba, Yasumichi,Yamashina, Naoko,Hara, Shoji,Suzuki, Akira
, p. 1757 - 1760 (2007/10/02)
(E)-(2-Bromoethenyl)dibromoborane, prepared readily by the bromoboration of acetylene with tribromoborane, can be used as an effective precursor for the stereoselective synthesis of (E)-1,2-disubstituted ethenes.
