Enhanced cooperative activation effect in the hydrolytic kinetic resolution of epoxides on [Co(salen)] catalysts confined in nanocages.

نویسندگان

  • Hengquan Yang
  • Lei Zhang
  • Lin Zhong
  • Qihua Yang
  • Can Li
چکیده

The solid catalyst with high catalytic activity and enantioselectivity in the hydrolytic kinetic resolution (HKR) of epoxides was prepared by confining Co(Salen) in the nanocage of SBA-16 through reducing the pore entrance size using a silylation method. It was found that the activity of the solid catalysts increased with the number of [Co(Salen)] molecules per nanocage increasing, and the solid catalyst with more than two chiral [Co(Salen)] molecules in one nanocage of SBA-16 exhibits much higher activity and enantioselectivity than the homogeneous [Co(Salen)] catalyst in the HKR of epoxides at low substrate/catalyst ratio. The significantly improved activity of the solid catalyst is due to a high local concentration of [Co(Salen)] in nanospace because of the enhanced cooperative activation effect of [Co(Salen)] molecules.

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

Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides.

The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co-X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co-OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the i...

متن کامل

Olefin metathesis as a tool for multinuclear Co(III)salen catalyst construction: access to cooperative catalysts.

The construction of novel (macrocyclic) multinuclear Co(III)salen catalysts is reported. Olefin metathesis has been used as a key construction tool for the multimetallic structures starting from versatile allyl-substituted salen scaffolds. The Co(III) complexes were tested in the hydrolytic kinetic resolution of (rac)-1,2-epoxyhexane and epoxide ring opening reactions using methanol as the nucl...

متن کامل

Mechanistic basis for high reactivity of (salen)Co-OTs in the hydrolytic kinetic resolution of terminal epoxides.

The (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides is a bimetallic process with a rate controlled by partitioning between a nucleophilic (salen)Co-OH catalyst and a Lewis acidic (salen)Co-X catalyst. The commonly used (salen)Co-OAc and (salen)Co-Cl precatalysts undergo complete and irreversible counterion addition to epoxide during the course of the epoxide hy...

متن کامل

Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen)Co(III) complexes. Practical synthesis of enantioenriched terminal epoxides and 1,2-diols.

The hydrolytic kinetic resolution (HKR) of terminal epoxides catalyzed by chiral (salen)Co(III) complex 1 x OAc affords both recovered unreacted epoxide and 1,2-diol product in highly enantioenriched form. As such, the HKR provides general access to useful, highly enantioenriched chiral building blocks that are otherwise difficult to access, from inexpensive racemic materials. The reaction has ...

متن کامل

Highly active oligomeric (salen)co catalysts for asymmetric epoxide ring-opening reactions.

Cooperative bimetallic catalysis has been documented in several recently reported asymmetric epoxide opening reactions that display second-order kinetic dependence on catalyst, specific requirements for multiple metal ions, and/or pronounced catalyst nonlinear effects.1 In such systems, one metal is proposed to serve as Lewis acid for epoxide activation and another as counterion for the nucleop...

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:
  • Angewandte Chemie

دوره 46 36  شماره 

صفحات  -

تاریخ انتشار 2007