Glueck, D. S. Transition metal complexes with C-stereogenic alkyl ligands and P-stereogenic analogues: Synthesis, configurational stability, stereochemistry of fundamental transformations, and intermediacy in catalysis. Adv. Organomet. Chem. 2025 in press.

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Abstract

 

Enantiomerically or diastereomerically enriched transition metal complexes bearing formally anionic, sp3-hybridized, C-stereogenic alkyl ligands ([M]-R⁎) are historically important for applications in determining the stereochemistry of fundamental steps in organometallic chemistry; isoelectronic P-stereogenic analogues ([M]-P⁎) have been studied more recently. These complexes are key intermediates in asymmetric catalysis, and the stereochemistry of their formation and reactions controls stereoselectivity. Understanding these processes with chiral catalysts may enable rational design of asymmetric transformations. This review covers their chemistry, including preparation by resolution or asymmetric synthesis (controlled by chiral substrates or chiral ligands), configurational stability, the stereochemistry of fundamental transformations, and their role in catalysis.  



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