Abstract
This Account describes the discovery and development of a family of organometallic
reagents derived from naturally occurring α-amino acids that have found widespread
use in the stereocontrolled synthesis of non-natural analogues of proteinogenic amino
acids. The general approach that we have taken involves the conversion of the side
chain of enantiomerically pure naturally occurring amino acids, such as serine, aspartic
acid and glutamic acid, into the corresponding primary alkyl iodide, followed by conversion
into the corresponding organozinc reagents. Subsequent palladium- or copper-catalysed
reactions of these reagents allow the synthesis of a wide variety of functionalised
α-, β- and γ-amino acid derivatives, without loss of stereochemical integrity. Insights
gained from spectroscopic and kinetic studies into the stability of functionalised
organozinc reagents are included.
1 Introduction
2 Preparation and Applications of α-Amino Acid Derived
2.1 Synthesis of Phenylalanine Derivatives
2.2 Preparation of β-Heteroaryl Alanine Derivatives
3 Cross-Couplings with Aryl Triflates, Bromides and
4 Cross-Couplings with Vinyl Triflates and Iodides
5 Preparation of Keto Amino Acids
6 Preparation and Applications of α-Amino Acid Derived
7 Preparation of Homologous Amino Acid Derived
8 Stability and Reactivity Studies of β- and γ-Amidozinc
9 Conclusions
Key words
amino acids - copper - cross-coupling - palladium - zinc
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