Synthesis and Applications of Tricarbonyliron Complexes of Dendralenes

Date

2011

Authors

Toombs-Ruane, Henry
Osinski, Nik
Fallon, Thomas
Wills, Cindy
Willis, Anthony
Paddon-Row, Michael
Sherburn, Michael

Journal Title

Journal ISSN

Volume Title

Publisher

Wiley-VCH Verlag GMBH

Abstract

[3]Dendralene and [4]dendralene are converted smoothly into tricarbonyliron complexes. The structures of four complexes analyzed by DFT and single-crystal X-ray analysis show that, in contrast to free hydrocarbons, complexed dendralenes prefer a roughly in-plane conformation. The complexes are stable towards Fe(CO)3 group migration up to 150 °C. The synthetic value of Fe(CO)3 complexation in the dendralene series is demonstrated through a variety of selective synthetic manipulations (Diels-Alder reaction, dipolar cycloaddition, Simmons-Smith cyclopropanation, dihydroxylation, olefin cross metathesis) that are not achievable by direct transformation of the free hydrocarbons. Application to the synthesis of a previously unreported, highly reactive linear/cross-conjugated hydrocarbon is also described. Simplicity through complexation: Tricarbonyliron complexes of dendralenes are readily prepared and stable. They allow the formation of products that cannot be accessed directly from dendralenes, including unprecedented structures (see scheme).

Description

Keywords

Keywords: Cyclopropanation; dendralenes; Density-functional calculations; Diels-Alder reaction; Dihydroxylation; Dipolar cycloadditions; Group migration; In-plane; metathesis; Olefin cross-metathesis; Single crystal X-ray analysis; synthesis design; Synthetic manip dendralenes; density functional calculations; hydrocarbons; metathesis; synthesis design

Citation

Source

Chemistry - An Asian Journal

Type

Journal article

Book Title

Entity type

Access Statement

License Rights

DOI

10.1002/asia.201100455

Restricted until

2037-12-31