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The Divalent Titanium Complex Ti(O‐ i ‐Pr) 4 /2 i ‐PrMgX as an Efficient and Practical Reagent for Fine Chemical Synthesis
Author(s) -
Sato Fumie,
Okamoto Sentaro
Publication year - 2001
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/1615-4169(20011231)343:8<759::aid-adsc759>3.0.co;2-m
Subject(s) - chemistry , intramolecular force , reagent , alkyne , titanium , nucleophilic acyl substitution , nucleophile , alkene , divalent , allylic rearrangement , combinatorial chemistry , vicinal , medicinal chemistry , organic chemistry , catalysis , acylation
This account describes synthetic transformations of unsaturated hydrocarbons, such as alkynes, alkenes, and dienes, mediated by the divalent titanium reagent Ti(O‐ i ‐Pr) 4 /2 i ‐PrMgX, which proceed via (ν 2 ‐alkene)‐ or (ν 2 ‐alkyne)‐titanium intermediates. Many of these transformations are otherwise difficult or require multi‐step reaction sequences. Since Ti(O‐ i ‐Pr) 4 and i ‐PrMgX are non‐toxic and available in bulk at low price, the reagent satisfies the qualifications for use in large‐scale synthesis. 1 Introduction 2 A General View of the Ti(O‐ i ‐Pr) 4 /2 i ‐PrMgX Reagent 3 Generation of an (ν 2 ‐Alkyne)Ti(O‐ i ‐Pr)2 and its Utilization as a Vicinal Vinylic Dianion 4 Preparation of Allyl‐ and Allenyltitanium Reagents and their Synthetic Utility 4.1 Allylic Titanium Reagents 4.2 Allenylic Titanium Reagents 5 Intramolecular Nucleophilic Acyl Substitution (INAS) Reactions Mediated by Ti(O‐ i ‐Pr) 4 /2 i ‐PrMgX 5.1 Scope of the Reaction 5.2 Synthetic Applications of the INAS Reaction 6 Intra‐ and Intermolecular Coupling of Olefins and Acetylenes 6.1 Intramolecular Reactions 6.2 Intermolecular Reactions 6.3 Tandem Inter‐ and Intramolecular Reactions 7 Summary and Outlook