Straightforward Synthesis of Allylated Keto Esters: The Palladium‐Catalysed Haloketone Alkoxycarbonylation/ Allylation Domino Reaction

Abstract

The palladium‐catalysed α‐chloro ketone methoxycarbonylation and allylic alkylation reactions can be efficiently combined to provide a new catalytic domino reaction. The first, carbonylative, step generates the β‐keto ester, which acts as the nucleophile in a subsequent allylation step. The use of allyl phenates in combination with Xantphos ligand are the key features allowing one to obtain the allylated β‐keto esters in good yields

Dual Platinum and Pyrrolidine Catalysis in the Direct Alkylation of Allylic Alcohols: Selective Synthesis of Monoallylation Products

“…Chemie and high selectivity (entries [2][3][4][5][6][7][8][9]. Notably, the branched allylic alcohol 1 j was efficiently converted into the linear monoallylation product 4 aa with the same 4/5 ratio (entry 10) as in the reaction of 1 a (entry 1).…”

“…Another synthetic method is the transitionmetal-catalyzed substitution reaction of activated allylic alcohol derivatives, such as allylic halides, carboxylates, and carbonates, via a p-allylmetal intermediate, the so-called Tsuji-Trost reaction. [2] In these reactions, however, undesirable overreactions may occur to give the diallylated [3] compound 5, and thus making it difficult to separate the desired monoallylation products from the reaction mixture. Although several highly mono-selective stoichiometric [4] and catalytic [5] reactions with some specific substrates have been reported, further development of mono-selective allylation with a broader substrate generality is in high demand.…”

Palladium‐Catalyzed Carbonylative Multicomponent Reactions

“…By combining palladium‐catalyzed alkoxycarbonylation with allylic alkylation, Sauthier and co‐workers achieved the four‐component synthesis of allylated β‐ketoesters (Scheme ) . The choice of phosphine ligand is the key to a successful reaction design.…”

A new xantphos-type ligand and its gold(I) complexes: Synthesis, structure, luminescence

“…This explains the structural variety of xantphos complexes, demonstrated by studies on its Pd [6], Pt [7], Rh [5] and Ir [8] complexes, in which it acts as a monodentate, a bidentate (P,P with cis or trans coordination mode) or a tridentate (P,O,P) ligand. Many of its Pd, Ru, Rh complexes proved to be efficient catalysts in homogeneous catalytic reactions [9,10]. Combined X-ray and catalytic studies on the complexes of xantphos and other diphosphines revealed that the catalytic effect depends on the P-M-P 'bite angle' [6,11,12].…”