Recent Developments in Pd(0)-Catalyzed Alkene Carboheterofunctionalization Reactions

Abstract

This review summarizes recent developments in palladium-catalyzed alkene carboalkoxylation and carboamination reactions. New synthetic methods that have been reported in the past four years are described, along with mechanistic issues and the influence of mechanism on product stereochemistry. The applications of these transformations to the synthesis of natural products and other biologically relevant compounds are also discussed.

Keywords: Alkenes; Carbocycles; Catalysis; Heterocycles; Palladium.

Figure 1

Common Ligands for Pd-Catalzyed Alkene Carboheterofunctionalization Reactions.

Scheme 1

Pd-Catalyzed Alkene Carboheterofunctionalization

Scheme 2

Catalytic Cycle: Syn-Heteropalladation

Scheme 3

Synthesis of (+)-Merobatzelladine B

Scheme 4

Synthesis of the Left-Wing Fragment of 11-epi-Azadirachtin I

Scheme 5

Synthesis of Tetrahydroindoloisoquinolines

Scheme 6

Synthesis of 8-Oxoprotoberberines

Scheme 7

Pd-catalyzed Carboamination/Diels Alder Reactions of 21

Scheme 8

Pd-catalyzed Carboamination/Diels Alder Reactions of 24

Scheme 9

Pd-catalyzed Carboamination/Diels Alder Reactions of 26

Scheme 10

Pd-catalyzed Carboamination Reactions of Alkylidenecyclopropanes

Scheme 11

Pd-catalyzed Carboalkoxylation Reactions of Hemiaminals

Scheme 12

Pd-catalyzed Carboalkoxylation Reactions of Aminals

Scheme 13

Asymmetric Pd-Catalyzed Reactions of N-Allylureas

Scheme 14

Asymmetric Desymmetrization of Diallylpyrrolidinyl Ureas

Scheme 15

Asymmetric Synthesis of Cyclic Sulfamides

Scheme 16

Asymmetric Synthesis of Tetrahydrofurans

Scheme 17

Asymmetric Synthesis of 6-Membered Bicyclic Nitrogen Heterocycles

Scheme 18

Asymmetric Synthesis of 6-Membered Bicyclic Oxygen Heterocycles

Scheme 19

Pd-Catalyzed Alkene Carbocyanation Reactions

Scheme 20

Pd-Catalyzed Insertion of Alkenes into β-Lactams

Scheme 21

Intermolecular Pd-Catalyzed Carboaminations of Dihydrofurans

Scheme 22

Intermolecular Asymmetric Pd-Catalyzed Carboalkoxylation of Dihydrofurans

Scheme 23

Pd-Catalyzed Intermolecular Alkene Aminocarbonylation

Scheme 24

Pd-Catalyzed Alkene Carboamination Reactions of O-Pentafluorobenzoyloximes

Scheme 25

Catalytic Cycle: anti-Heteropalladation

Scheme 26

Stereoselective syn vs. anti-Heteropalladation of Sulfamide 76

Scheme 27

Influence of Reaction Conditions on Product Stereochemistry

Scheme 28

Stereoselective syn vs. anti-Heteropalladation of Urea 78

Scheme 29

Pd-Catalyzed Carboamination of N-Allylsulfamides

Scheme 30

Pd-catalyzed Regioselective Alkyne Carboalkoxylation

Scheme 31

Influence of syn- vs. anti-Aminopalladtion on 1,3-Asymmetric Induction.

Scheme 32

Pd-Catalyzed Synthesis of Bicyclic Sulfamides

Scheme 33

Pd-catalyzed Carboamination of N-Tosyl-γ-aminoalkenes

Scheme 34

Formal Synthesis of (±)-Aphanorphine

Scheme 35

Pd-Catalyzed Carboamination of N-Tosyl-N’-propargyl Guanidines

Scheme 36

Synthesis of 2-Aminoimidazole Natural Products

Scheme 36

Pd-catalyzed Synthesis of Dihydrobenzofurans

Scheme 37

Synthesis of Pyrrolidinyl Cyclopropanes

Scheme 38

Pd-Catalyzed Coupling of Unsaturated Alcohols with Alkynamides

Scheme 39

Mechanistic Possibilities

Scheme 40

Pd-Catalyzed Coupling of 117 with Alkenes

Scheme 41

Pd-Catalyzed Macrolactonization

Scheme 42

Synthesis of 9-Dimethylneopeltolide

Scheme 43

Cascade Alkene Carboalkoxylation/Heck Reactions

Scheme 44

Asymmetric Synthesis of 2-Aminoindane Derivatives

Scheme 45

Mechanism of Aminoindane Formation

Scheme 46

Stereochemical Model

Scheme 47

Pd-catalyzed Carboamination Reactions of Allenes

Scheme 48

Intramolecular Pd-catalyzed Carboamination Reactions of Dienyl β-Ketoamides