Ring expansion of 5- to 6-member zirconacycles by carbenoid insertion

A wide range of carbenoids (1-lithio-1-halo species), including those with α-SiR 3, OEt, SPh, SO 2Ph, P(O)(OEt) 2, and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert t...

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Bibliographic Details
Published inTetrahedron Vol. 60; no. 6; pp. 1401 - 1416
Main Authors Dixon, Sally, Fillery, Shaun M., Kasatkin, Aleksandra, Norton, David, Thomas, Emma, Whitby, Richard J.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 02.02.2004
Elsevier
Subjects
Carbenoid
Chemistry
Chemistry, Organic
Insertion
Multi-component
Physical Sciences
Ring expansion
Science & Technology
Zirconacycle
Zirconium
Insertion
Zirconium
Zirconacycle
Carbenoid
Multi-component
Ring expansion
TANDEM INSERTION
zirconacycle
ALDEHYDES
ALKYNES
CARBON BOND FORMATION
METAL-PROMOTED CYCLIZATION
LITHIUM CHLOROALLYLIDE
ring expansion
ZIRCONOCENE
insertion
zirconium
CONVERGENT SYNTHESIS
multi-component
DERIVATIVES
carbenoid
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Summary:A wide range of carbenoids (1-lithio-1-halo species), including those with α-SiR 3, OEt, SPh, SO 2Ph, P(O)(OEt) 2, and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert to afford 6-member zirconacycles with an alkylidene substituent next to the metal. Unexpected double insertion of some carbenoids, and evidence for endocylic β-hydride transfer processes provide additional mechanistic interest. Graphic
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2003.09.056