Cyclization Strategies in Carbonyl-Olefin Metathesis: An Up-to-Date Review

Abstract

The metathesis reaction between carbonyl compounds and olefins has emerged as a potent strategy for facilitating swift functional group interconversion and the construction of intricate organic structures through the creation of novel carbon-carbon double bonds. To date, significant progress has been made in carbonyl-olefin metathesis reactions, where oxetane, pyrazolidine, 1,3-diol, and metal alkylidene have been proved to be key intermediates. Recently, several reviews have been disclosed, focusing on distinct catalytic approaches for achieving carbonyl-olefin metathesis. However, the summarization of cyclization strategies for constructing aromatic heterocyclic frameworks through carbonyl-olefin metathesis reactions has rarely been reported. Consequently, we present an up-to-date review of the cyclization strategies in carbonyl-olefin metathesis, categorizing them into three main groups: the formation of monocyclic compounds, bicyclic compounds, and polycyclic compounds. This review delves into the underlying mechanism, scope, and applications, offering a comprehensive perspective on the current strength and the limitation of this field.

Keywords: bicyclic compounds; carbonyl–olefin metathesis; cyclization; monocyclic compounds; polycyclic compounds.

Figure 1

Strategies for carbonyl–olefin metathesis.

Figure 2

The classification of carbonyl–olefin metathesis.

Scheme 1

The synthesis of cycloalkenes via carbonyl–olefin metathesis reaction.

Scheme 2

Olefinic ester ring-closing metathesis: using a reduced titanium akylidene.

Scheme 3

Diversity-oriented synthesis of carbocyclic.

Scheme 4

Catalytic intramolecular carbonyl–olefin reaction.

Scheme 5

Iron(III)-catalyzed carbonyl–olefin metathesis.

Scheme 6

FeCl₃-catalyzed ring-closing carbonyl–olefin metathesis.

Scheme 7

The synthesis of 3-aryl-2,5-dihydropyrroles.

Scheme 8

Catalytic carbonyl–olefin metathesis of aliphatic ketones.

Scheme 9

Catalytic, transannular carbonyl–olefin metathesis reactions.

Scheme 10

Tetrahydropyridines via FeCl₃-catalyzed carbonyl–olefin metathesis.

Scheme 11

Gallium-catalyzed tandem carbonyl–olefin metathesis/transfer hydrogenation.

Scheme 12

Super-electrophilic aluminum (III)-ion pair-catalyzed carbonyl–olefin metathesis.

Scheme 13

AuCl₃-catalyzed ring-closing carbonyl–olefin metathesis.

Scheme 14

The synthesis of cyclopentene mediated by bis(perchlorocatecholato) germane.

Scheme 15

InCl₃-catalyzed intramolecular carbonyl–olefin metathesis.

Scheme 16

Intramolecular cycloreversion mediated by BF₃.Et₂O.

Scheme 17

Brønsted acid-catalyzed carbonyl–olefin metathesis.

Scheme 18

The synthesis of 2,5-dihydropyrroles via carbonyl–olefin metathesis reactions.

Scheme 19

Carbonyl–olefin metathesis catalyzed by HFIP and pTSA.

Scheme 20

Brønsted acid-catalyzed intramolecular carbonyl–olefin metathesis reactions.

Scheme 21

Tropylium-promoted carbonyl–olefin metathesis reactions.

Scheme 22

Carbonyl–olefin metathesis catalyzed by molecular iodine.

Scheme 23

Iodonium-catalyzed carbonyl–olefin metathesis reactions.

Scheme 24

Al-catalyzed carbonyl–olefin metathesis reactions.

Scheme 25

Au-catalyzed carbonyl–olefin metathesis reactions.

Scheme 26

Titanocene alkylidene complex-catalyzed carbonyl–olefin metathesis reactions.

Scheme 27

The construction of the JKL, OPQ, and UVW ring systems of Maitotoxin.

Scheme 28

Approach to 1,4-dihydroquinoline via carbonyl–olefin metathesis reactions.

Scheme 29

Approach to fused ether ring systems via carbonyl–olefin metathesis reactions.

Scheme 30

Olefinic ester cyclizations using Takai–Utimoto-reduced titanium alkylidenes.

Scheme 31

Ti alkylidenes mediated carbonyl–olefin metathesis reactions.

Scheme 32

Olefinic lactone cyclization to macrocycles.

Scheme 33

Olefinic amide and olefinic lactam cyclizations.

Scheme 34

Photoprotolytic-mediated carbonyl–olefin metathesis reactions.

Scheme 35

The synthesis of bicyclic compounds via photoinduced intramolecular cyclization.

Scheme 36

The synthesis of bicyclic compounds mediated by TfOH.

Scheme 37

BF₃.Et₂O mediated intramolecular carbonyl–olefin metathesis.

Scheme 38

Carbocation-catalyzed ring-closing aldehyde–olefin metathesis.

Scheme 39

Hydrazine-catalyzed ring-closing carbonyl–olefin metathesis.

Scheme 40

Synthesis of 1,2-dihydroquinolines via ring-closing carbonyl–olefin metathesis.

Scheme 41

Ring-closing carbonyl–olefin metathesis catalyzed by titanium reagents.

Scheme 42

Olefin metathesis in cyclic ether formation.

Scheme 43

The application of olefin metathesis.

Scheme 44

Two-directional olefinic ester ring-closing metathesis.

Scheme 45

The synthesis of tricycle compound.

Scheme 46

Polycyclic aromatic hydrocarbons via iron(III)-catalyzed carbonyl–olefin metathesis.

Scheme 47

Synthesis of angucycline derivatives using carbonyl–olefin metathesis.

Scheme 48

Brønsted acid-catalyzed carbonyl–olefin metathesis. A represents the yield obtained under condition 1); B represents the yield obtained under condition 2); C represents the yield obtained under condition 3).

Scheme 49

Hydrazine-catalyzed ring-closing carbonyl–olefin metathesis.