Asymmetric palladium-catalysed intramolecular Wacker-type cyclisations of unsaturated alcohols and amino alcohols

Abstract

The palladium (II)-catalysed reactions of alkenols and aminoalkenols such as oxycarbonylations or bicyclisations are powerful methods for the construction of oxygen and nitrogen-containing heterocyclic compounds. This review highlights recent progress in the development of the asymmetric palladium(II)-catalysed Wacker-type cyclisations of unsaturated polyols and aminoalcohols. The scope, limitations, and applications of these reactions are presented.

Scheme 1

Palladium-catalysed intramolecular Wacker-type cyclisations of unsaturated alcohols and amino alcohols.

Scheme 2

Pd(II)-catalysed Wacker-type oxidative heterocyclisations.

Scheme 3

AsymmetricPd(II)-catalysed Wacker-type cyclisation of allylphenol 1a using (S,S)-boxax ligands.

Scheme 4

Pd(II)-catalysed asymmetric aerobic oxidative cyclisation of allylphenol 3.

Figure 1

Model figures of diastereomeric monometallic and bimetallic complexes with tetraoxazoline ligands.

Scheme 5

Asymmetric intramolecular Wacker-type cyclisation of 1 using tetraoxazoline 5c-Pd(OCOCF₃)₂ catalyst.

Scheme 6

Aza-Wacker-type cyclisation reaction of o-allylanilines 7.

Scheme 7

Pd^II-SPRIX-catalysed cyclisation reaction of alkenyl alcohols 11, 2-alkenyl-1,3-diketones 13 and 4-alkenoic acids 15.

Scheme 7

Pd^II-SPRIX-catalysed cyclisation reaction of alkenyl alcohols 11, 2-alkenyl-1,3-diketones 13 and 4-alkenoic acids 15.

Scheme 8

Asymmetric domino Wacker-Heck reaction of alkenyl phenol 17 and methyl vinyl ketone 18 using (S,S)-Bn-boxax ligand.

Scheme 9

Asymmetric intramolecular domino Wacker-Heck reaction of dialkenyl alcohol 20 using spiro bis(isoxazoline) and spiro (isoxazole-isoxazoline) ligands.

Scheme 10

Asymmetric domino Wacker-Heck bicyclisation of 2-allylanilide substrates using (−)-sparteine.

Scheme 11

Asymmetric domino Wacker-Heck reaction in the synthesis of pyrrolizines/ pyrroloindoles using (M,S,S)-ⁱPr-SPRIX ligand 9c.

Scheme 12

Mechanism of palladium-catalysed carboetherification and carboamination reactions.

Scheme 13

Asymmetric palladium-catalysed carboamination reaction for the synthesis of enantiomerically enriched pyrrolidines using (R)-Siphos-PE ligand.

Scheme 14

Synthesis of (–)-tylophorine.

Scheme 15

Synthesis of (+)-aphanorphine.

Scheme 16

Asymmetric carboamination reaction of N-allyl urea derivatives with 1-bromo-4-tert-butylbenzene using (S)-Siphos-PE ligand.

Scheme 17

Asymmetric carboamination reaction of substrates 31a,b with different aryl halides using (S)-Siphos-PE ligand.

Scheme 18

Asymmetric cyclisation-carbonylation of meso-2-alkyl-2-propargyl-1,3-cyclohexane-diols 32 and -1,3-diones 34 using Pd(II)-[box] catalysts.

Scheme 19

Parallel kinetic resolution of propargyl ketols 38 using Pd(II)-[box] catalyst.

Scheme 20

Asymmetric domino reaction of alkenes 41–42 and phenyl ethers 45 employing (S,S)-Bn-boxax.

Scheme 21

Asymmetric aminocarbonylation of N-(2,2-dimethylpent-4-enyl)-p-toluenesulfonamide 47 using Pd(II)-[SPRIX] catalysts.

Scheme 22

Kinetic resolution of alkene-1,3-diols (±)-49 in an asymmetric Pd(II)-catalysed oxycarbonylation.

Scheme 23

Kinetic resolution of pent-4-ene-1,3-diol (±)-49a by Pd(II)-catalysed oxycarbonylation in ionic liquids.

Scheme 24

Palladium(II)-catalysed oxycarbonylation of meso-diols 55 and 57, and pseudo-C₂-symmetric enitol 56.

Scheme 25

Kinetic resolution of N-protected 1-aminopent-4-ene-3-ols (±)-63 in the Pd(II)-catalysed amidocarbonylation and Pd(II)-catalysed amidocarbonylation of alkenylureas 65.