Two Sterically Encumbered 1,3,2‐Dioxaphospholanes – Reactions,Comparison of Crystal Structures and Computational Explanations

3,4,5,6‐Tetrachlorobenzo‐3‐(2,4,6‐tri‐tert‐butylphenyl)‐1,3,2‐dioxaphospholane ( 2 ) and benzo‐3‐(2,4,6‐tri‐tert‐butylphenyl)‐1,3,2‐dioxaphospholane ( 4 ), in which the reactive P^III‐center lies close to the sterically demanding Mes* group (Mes* = 2,4,6‐tri‐tert‐butylphenyl), were prepared from Mes*–Br and the corresponding P‐chloro‐phospholane. Compounds 2 and 4 reacted with various oxidants, azides, MeSO₃CF₃ or [(tht)AuCl] (tht = tetrahydrothiophene) to give the expected products. All crystal structures of the products display a strongly distorted Mes* system with a boat conformation of the phenyl ring and appreciable out‐of‐plane deviations of phosphorus and the ortho‐tert‐butyl groups to opposite sides of the ring. Quantum chemical calculations at the DFT (density functional theory) level of theory were used in order to discriminate between intra‐ and intermolecular forces, which are responsible for these distortions.     

Synthese und Molekülstruktur chiraler Bis(1,3,2‐dioxaphospholane)

Synthesis and Molecular Structure of Chiral Bis(1,3,2‐dioxaphospholanes) Bisphosphites of the general type C₂O₂POC_nOPO₂C₂ containing chiral building blocks both in the five‐membered C₂O₂P rings and in the OC_nO bridge were prepared from 2‐chloro‐1,3,2‐dioxaphospholanes and chiral diols in the presence of a base. The molecular structure of compound 10 , which was obtained from 2‐chloro‐(4R,5R)‐4,5‐dimethyl‐1,3,2‐dioxaphospholane and (R)‐1,1′‐binaphthalin‐2,2′‐diol, was determined by X‐ray crystallography.     

Zirconium-catalyzed preparation of aluminacyclopentanes and synthesis of five-membered carbo- and heterocycles

Novel ‘one-pot’ catalytic methods for the synthesis of cyclopentanols, tetrahydrothiophenes, silacyclopentanes and phospholanes are based on successive transformations of olefins and organoaluminium compounds (R₂AlR′) in the presence of Cp₂ZrCl₂ catalyst. In situ generated aluminacyclopentanes serve as common intermediates in these processes.