Cp₂Ti(III)Cl and Analogues as Sustainable Templates in Organic Synthesis

^† These authors contributed equally to this work

Abstract

This short review aims to provide an overview of the use of Cp₂Ti(III)Cl and other related titanocene(III) species as coordinating reagents­ in template reactions in the selective preparation of C–C and C–O bonds. These complexes are able to assemble two components to produce powerful reactions possessing high regio-, chemo-, diastereo-, and enantioselectivity. The titanocene templates are divided into five structural types. The chemical transformations by these valuable templates, the substrate scope and mechanistic insights will also be described.

1 Introduction

2 Precedents for the Coordination of Ti(III) Species to Heteroatoms

2.1 Coordination of Compounds with Hydrogen–Heteroatom Bonds to Ti(III) Species

2.2 Coordination of Halogens to Ti(III) Species

3 Types of Titanocene Templates

4 Template Type I Mediated Organic Reactions

4.1 Methylenecyclopropanation of Allylic Alcohols

4.2 Base-Free O-Acylation of Alcohols and Phenol

4.3 Epoxidation of Allylic Alcohols

5 Template Type II Mediated Organic Reactions

5.1 Ketone–Nitrile Cross-Coupling Reactions

5.2 Imine–Nitrile Cross-Coupling Reactions

5.3 Reductive Alkylation of Enones with Activated Alkenes

6 Template Type III Mediated Organic Reactions

6.1 Pinacol Coupling of Ketones

7 Template Type IV Mediated Organic Reactions

7.1 Michael-Type Addition of Aldehydes to Conjugated Enals

7.2 Allylation, Crotylation, and Prenylation

7.3 Barbier-Type Progargylation and Allenylation

8 Template Type V Mediated Organic Reactions

8.1 Protection of Alcohols as 2-O-THF and 2-O-THP Ethers

8.2 Pinacol Coupling of Aldehydes

8.3 McMurry Couplings

9 Conclusions and Perspectives

Key words

titanocene - template - catalysis - radical reactions - titanium

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