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Synlett 2002(7): 1043-1054
DOI: 10.1055/s-2002-32571
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Coordination Compounds as Synthetic Building Blocks

Yitzhak Tor*
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0358, USA
Fax: +1(858)5345383; e-Mail: ytor@ucsd.edu;
Further Information

Publication History

Received 6 September 2001
Publication Date:
07 February 2007 (online)

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Abstract

Transition metal complexes encompass a unique pool of building blocks with diverse stereochemical, electrochemical and photophysical features. Despite the current interest in employing polypyridine-containing coordination compounds for the fabrication of functional assemblies, their full potential as synthetic building blocks remains under-utilized. The account discusses the inspiration and rationale for advancing the synthetic chemistry of coordination compounds and presents recent developments where the complexity of these intriguing ‘inorganic’ building blocks is increased via ‘organic’ transformations.

1 Introduction

2 Why Metal-Containing Materials?

3 Why Develop the Organic Chemistry of Coordination
Compounds?

4 Selecting a Parent Ligand

5 Functionalizing 1,10-Phenanthroline

6 Coordination Compounds as Building Blocks

6.1 Cross-Coupling Reactions

6.2 Radical Transformations

6.3 Nucleophilic Aromatic Substitutions

7 Where do we go from here?

8 Summary

Key words

coordination compounds - cross coupling - metal-containing materials - nucleophilic aromatic substitutions - 1,10-phenanthroline

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The terms ‘organic’ and ‘inorganic’ are placed in quotation marks for obvious reasons. Coordination compounds, where an ‘inorganic’ ion is surrounded by ‘organic’ ligands represent the ultimate hybrid of disciplines.

5

Ref. [1a] , p. 56.

27

The final cyclization step is a Skraup reaction between 8-amino-3-bromoquinoline and a protected hydrate of bromoacrolein. It affords 3,8-dibromo-1,10-phenanthroline in 4.4% yield.

31

Typical yields are 25-35% for 1 and 20-25% for 2. Altering the reaction conditions results in changes in the ratio between the mono and dibromo derivatives, as well as the amounts of higher brominated side products.

33

Some of these interesting brominated phenanthrolines were also synthesized by Case. See ref. [26]

40

For example, the reaction of 4 with 4-ethynyltoluene gave 8 in 91% isolated yield after 1 h at r.t.

46

Weizman, H.; Tor, Y. unpublished results.

50

Hurley, D. J.; Tor, Y. unpublished results.

64

Glazer, E. C.; Tor, Y. submitted.