Pd(II)-Catalyzed Carbonylation of Unsaturated Polyols and Aminopolyols

Aminohydroxylation of divinylcarbinol and its application to the synthesis of bicyclic hydroxypyrrolidine and aminotetrahydrofuran building blocks

“…1) called for enantioselective preparation of the (2S,3R)-2-N-R 1 -aminopent-4-ene-1,3-diol (anti-III ) as the key substrate, which is accessible from divinylcarbinol IV employing the Sharpless asymmetric aminohydroxylation as the source of chirality. For the second key step, being oxycarbonylating bicyclisation of anti-III, we took advantage of recent progress in Pd(II)-catalysed carbonylation of unsaturated polyols, which turned out bicyclic lactones with excellent 1,5-threo selectivity (Gracza et al, 1991;Jäger et al, 1997;Gracza & Jäger, 1992, 1994Dixon et al, 1999;Babjak et al, 2002Babjak et al, , 2005. The study directed towards the synthesis of the lactone l-arabino-II started with aminohydroxylation of divinylcarbinol (DVC).…”

“…Previous investigations in our laboratory have demonstrated that the Pd(II)-catalysed oxy-and amidocarbonylation of unsaturated polyols and amino polyols represent an efficient entry to cis-fused 5-membered bicyclic lactones (Gracza et al, 1991;Jäger et al, 1997;Hümmer et al, 1997). This methodology has been used as the key step in a number of natural product syntheses (Gracza & Jäger, 1992, 1994Dixon et al, 1999;Babjak et al, 2002Babjak et al, , 2005Karlubíková et al, 2011).…”

Asymmetric Palladium-Catalysed Intramolecular Wacker-Type Cyclisations of Unsaturated Alcohols and Amino Alcohols

“…Palladium(II)-catalysed cylisations of unsaturated alcohols, amines and other suitable substrates accompanied by the insertion of carbon monoxide provide a simple and straightforward access to one-carbon homologated esters, lactones and amides [1,2,6,29,30,31,32,33,34]. These domino processes have proven particularly useful for stereoselective construction of a range of oxygen and nitrogen-containing heterocyclic compounds [7,8,9,10,11,12,13,14,15]. Such a transformation of enantiomerically pure substrates has found numerous applications as the key step in the total syntheses of natural compounds [17,18,25,26,27,28,29].…”

“…Today, there are numerous applications of these transformations in the preparation of a large array of the useful products. Among them, an intramolecular oxidative cyclisation, referred to as the Wacker-type cyclisation, is one of the most versatile methods for the preparation of heterocycles [5,6,7]. Particularly, palladium(II)-catalysed reactions of unsaturated alcohols and amino alcohols such as oxy-/aminocarbonylations [8,9,10,11,12,13,14,15], bicyclisations [16,17,18] and domino cyclisation-cross couplings [19,20,21,22,23] serve as a potent stereoselective methods for the construction of oxa-/azaheterocyclic structures found in many natural or biologically relevant compounds [19,20,21,24,25].…”

“…Trapping of the intermediate A by other nucleophilic species provides oxa/azaheterocyclic compounds D linked with various substituents. Although a number of reviews on palladium-catalysed oxidative cyclisation and issues of stereochemical control already exist [3,4,5,6,7,22,23,24,26,27,28,29,30,31,32,33,34], no general summary on the asymmetric versions of the Pd(II)-catalysed Wacker-type cyclisation of unsaturated alcohols and aminoalcohols has been published. Considering the great potential for application of these methods to the synthesis of biologically active targets and for the extension to the synthesis of optically pure saturated heterocycles, we report here a summary of the main achievements in this area.…”