Bulky Phosphinines: From a Molecular Design to an Application in Homogeneous Catalysis
抄録
<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 CH 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>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 19 (27), 8991-9004, 2013-05-13
Wiley