The Addition, Cyclization And Rearrangement Of Functionalized Olefins And Their Derivatives

The dissertation mainly focuses on the introduction of the corresponding functional groups to α,β-unsaturated carbonyl compound at the different positions. And developed reactions in the presence of transition metal catalysis, iminium catalysis or the Lewis acid catalysis.In the first part, by introducing one or two alkynyl groups in the α-position of the unsaturated carbonyl compounds, some palladium-catalyzed domino cyclization reactions were designed and achieved.A PdⅡ-catalyzed three-component domino reaction of alkynyl-alken-ones with nucleophiles and vinyl ketones or acrolein leading to tetrasubstituted furans with100%atom-economy was developed.An atom-economic palladium(II)-catalyzed three-component domino reaction of diyne-enone with nucleophiles and vinyl ketones or acrolein was realized, leading to multi-functional2,3-cyclo[b]furan along with a stereodefined tetrasubstituted olefin.A novel palladium(II)-catalyzed oxidative domino reaction by combination of direct C-H functionalization of indoles with cascade cyclizations of diyne-enones was achieved using air as the oxidant, which provides a rapid access to novel indole-furan polyheterocycles.In the second part, by introducing the corresponding substituent in the β-position of the unsaturated carbonyl compound, the organocatalytic asymmetric conjugate addition to isatylidene-3-acetaldehydes was demonstrated.A novel enantioselective synthesis of3,3’-disubstituted oxindoles by organocatalytic conjugate addition of malonates to isatylidene-3-acetaldehyde was realized with high yield and excellent enantioselectivity. This transformation is easily scaled up to a gram scale. Using the method established, we enantioselective synthesized three core skeletons of indoline-derived alkaloids and achieved asymmetric total synthesis of (-)-debromoflustramine E in a quite short route.Asymmetric organocatalytic conjugate addition of indole to isatylidene-3-acetaldehyde has been well established, which provides a facile access to oxindoles bearing all-carbon quaternary stereocenters at the3-position with high enantioselectivity. It’s the first example of using buffer to enhance the enantioselectivity in the amine-catalyzed Michael addition. This transformation is easily scaled up to gram scale. We also applied the method to the formal total synthesis of (-)-chimonanthine and core structure construction of (+)-gliocladin C.In the third part, we converted the unsaturated carbonyl compound to epoxides and controlled its selective ring-opening in the presence of Lewis acid.An efficient [3+2] cycloaddition reaction of alkynes with an oxirane motif by Lewis acid catalyzed selective C-C bond cleavage was realized in high yields with excellent regioselectivities. Furthermore, the resulting2,5-dihydrofuran can be easily converted to synthetic useful furan,2,3-dihydrofuran, tetrahydrofuran, and2,5-dihydrofuranon.A Lewis acid catalyzed tandem selective cleavage of C-C bond, rearrangement and decarbonylation reaction was developed to give C-3aryl oxindoles. Unlike with the traditional mode, the C-O bond cleavage at the a-position instead of^-position of the carbonyl groups.