Affiliation:
1. Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia
Abstract
Brice Bosnich, an Australian inorganic chemist, graduated from the University of Sydney and obtained his PhD at the Australian National University, Canberra. He then worked successively at University College London, the University of Toronto and the University of Chicago. He had an abiding interest in stereochemistry and its relationship with chemical reactivity, and in the chirality and optical activity of coordination and organometallic complexes, mainly those of the d-block elements. His early studies concerned the topological and conformational behaviour of classical coordination compounds, mainly of cobalt(III), and made extensive use of the technique of circular dichroism. He put this background to elegant use in perhaps his most distinctive work, namely, the design and synthesis of a
C
2
-symmetric ditertiary phosphine, (
S
,
S
)-chiraphos, the rhodium(I) complex [Rh{Ph
2
PCH(CH
3
)CH(CH
3
)PPh
2
}]
+
of which catalysed efficiently the homogeneous hydrogenation of prochiral enamides to amino acids in high optical purity. Bosnich traced the high enantioselectivity to the chiral array of P-phenyl substituents that is generated on coordination of (
S
,
S
)-chiraphos. In principle, catalytic enantioselective synthesis represents a powerful and economic method of introducing chirality into the synthesis of biologically active molecules, which, since the thalidomide tragedy, are required to be marketed only in optically pure forms. Dissymmetric ligands similar to (
S
,
S
)-chiraphos are now routinely employed in this type of synthesis. Bosnich developed several other enantioselective processes based on organo-transition metal chemistry. He also had several quasi-theoretical interests, including the possible use of circular dichroism to determine the absolute configuration of chiral metal complexes, and the development of a molecular mechanics force field for metallocenes. He maintained a strong interest in the properties of multimetallic proteins and devoted much effort to the construction of chiral binucleating ligands. During the 7–8 years before his retirement from the University of Chicago in 2006, he shifted his research to supramolecular recognition by suitably designed metal complexes.