Catalytic asymmetric addition of carbon dioxide to propylene oxide with unprecedented enantioselectivity.

نویسندگان

  • Albrecht Berkessel
  • Marc Brandenburg
چکیده

New chiral catalyst systems were developed for the reaction of carbon dioxide with propylene oxide (PO) at atmospheric pressure to generate enantiomerically enriched propylene carbonate (PC). The best selectivity was achieved with a Co(III)(salen)-trifluoroacetyl complex and bis(triphenylphosphoranylidene)ammonium fluoride (PPN+F-) as catalysts, affording PC in 40% yield and 83% ee (selectivity factor = 19). In addition, PC was prepared for the first time by kinetic resolution of PO with tetrabutylammonium methyl carbonate (TBAMC, nBu4N+ (-)OOCOMe). With TBAMC as "activated CO2", up to 71% ee was obtained.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Catalytic Asymmetric Cycloaddition of Carbon Dioxide and Propylene Oxide Using Novel Chiral Polymers of BINOL-Salen- Cobalt(III) Salts

Four new chiral polymers of BINOLSalen-cobalt ACHTUNGTRENNUNG(III) salt complexes have been designed, synthesized and applied to the direct fabrication of chiral propylene carbonate from racemic propylene oxide. The (R/S)-polymer catalyst 2 and (S/R)-polymer catalyst 4 exhibit better enantioselectivity than the (R/R)-polymer catalyst 1 and the (S/S)-polymer catalyst 3 and have been recovered an...

متن کامل

Asymmetric catalytic synthesis of polyketones and polycarbonates*

Two examples are presented for the synthesis of optically active polymers with main-chain chirality from achiral monomers using chiral metal-complexes as catalysts. Asymmetric alternating copolymerization of α-olefins with carbon monoxide provided optically active polyketones when catalyzed by an (R,S)-BINAPHOS–Pd complex. From propene and CO, highly isotactic polyketone with high enantioselect...

متن کامل

Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids and Their Derivatives to Electron Deficient Olefins

Asymmetric 1,4-arylation and -alkenylation was achieved by use of organoboronic acids or their derivatives in the presence of a rhodium catalyst coordinated with binap ligand. The reaction conditions are unique in that it is usually carried out in an aqueous solvent at 100 °C. The scope of this asymmetric addition is very broad, a,b-unsaturated ketones, esters, 1-alkenylphosphonates, and 1-nitr...

متن کامل

Synergistic hybrid catalyst for cyclic carbonate synthesis: remarkable acceleration caused by immobilization of homogeneous catalyst on silica.

The catalytic activity of phosphonium salts towards cyclic carbonate synthesis from propylene oxide and CO2 has been enormously enhanced by their immobilization onto silica that itself has no catalytic activity.

متن کامل

Probing catalytic activity of halide salts by electrical conductivity in the coupling reaction of CO2 and propylene oxide.

In the water-assisted coupling reaction of CO(2) and propylene oxide (PO) catalyzed by halide salts, the PO conversion was closely correlated with the electrical conductivity, suggesting that simple conductivity measurements might be used as a potential method for the selection of the catalyst.

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Organic letters

دوره 8 20  شماره 

صفحات  -

تاریخ انتشار 2006