Bulky Phosphinines: From a Molecular Design to an Application in Homogeneous Catalysis

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<jats:title>Abstract</jats:title><jats:p>The design and preparation of an asymmetrically substituted and bulky phosphinine was achieved by introducing sterically demanding substituents into specific positions of a rigid phosphorus‐heterocyclic framework. Compound <jats:bold>5</jats:bold> shows, at the same time, axial chirality and a sufficiently high energy barrier for internal rotation to prevent enantiomerization. Both enantiomers of <jats:bold>5</jats:bold> were isolated by means of chiral analytical HPLC, and their absolute configurations could be assigned by combining experimental data and DFT calculations. Despite its substitution pattern, <jats:bold>5</jats:bold> can still coordinate to transition‐metal centers through the lone pair of electrons on the phosphorus atom. Rapid CH activation on the adjacent aryl substituent at the 2‐position of the phosphorus heterocycle was achieved by using [{Cp*IrCl<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>] (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of <jats:bold>5</jats:bold> was applied as a π‐accepting low‐coordinate phosphorus ligand in the Rh‐catalyzed hydroformylation of <jats:italic>trans</jats:italic>‐2‐octene, which showed a clear preference for the formation of 2‐methyloctanal.</jats:p>

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