Catalytic (asymmetric) methylene transfer to aldehydes.

نویسندگان

  • Alessandro Piccinini
  • Sarah A Kavanagh
  • Paul B Connon
  • Stephen J Connon
چکیده

An investigation into the poor activity of sulfides as catalysts for sulfonium-ylide-mediated methylene transfer to aldehydes has indicated that ylide formation is the problematic catalytic cycle step. Alkylation with traditional electrophiles does not proceed with sufficient efficiency to allow the sulfide to be used catalytically. Methyl triflate rapidly alkylates cyclic thiolanes under mild conditions, allowing their use in efficient aldehyde epoxidation reactions (in conjunction with phosphazene bases) at loadings as low as 10 mol %.

برای دانلود رایگان 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

Highly enantioselective ylide-mediated synthesis of terminal epoxides.

The highly efficient asymmetric epoxidation of aldehydes by methylene transfer is now possible using new sulfonium salts.

متن کامل

Catalytic enantioselective aryl transfer to aldehydes using chiral 2,2'-bispyrrolidine-based salan ligands.

Chiral C₂-symmetric diamines have emerged as versatile auxiliaries or ligands in numerous asymmetric transformations. Chiral 2,2'-bispyrrolidine-based salan ligands were prepared and applied to the asymmetric aryl transfer to aldehydes with arylboronic acids as the source of transferable aryl groups. The corresponding diarylmethanols were obtained in high yields with moderate to good enantiosel...

متن کامل

Catalytic asymmetric addition reactions leading to carbon–carbon bond formation: Phenyl and alkenyl transfer to aldehydes and alkynylation of -imino esters*

Optically active tertiary aminonaphthol ligands were obtained by a new, convenient procedure and were found to catalyze the enantioselective alkenyl and phenyl transfer to aldehydes in high yields and excellent enantiomeric excesses (ee’s). The catalytic asymmetric introduction of alkynyl functionality to α-amino acid derivatives was realized by the direct addition of terminal alkynes to α-imin...

متن کامل

Preparation of Mesoporous Silica-Supported Chiral Amino Alcohols for the Enantioselective Addition of Diethylzinc to Aldehyde and Asymmetric Transfer Hydrogenation to Ketones

Optically active (−)-ephedrine, (−)-norephedrine, and (−)-prolinol were immobilized onto cubic mesoporousMCM-48 silica.The immobilized amino alcohols served as a heterogeneous chiral catalyst for the asymmetric addition of diethylzinc to aldehydes and transfer hydrogenation to ketones. The developed catalytic process yielded optically enriches secondary aromatic alcohols with 92–99% conversion ...

متن کامل

Direct catalytic asymmetric aminoallylation of aldehydes: synergism of chiral and nonchiral Brønsted acids.

The development of a catalytic asymmetric method for the direct aminoallylation of aldehydes is described that gives high asymmetric inductions for a broad range of substrates including both aromatic and aliphatic aldehydes. This method allows for direct isolation of unprotected analytically pure homoallylic amines without chromatography. The unique catalyst system developed for this process in...

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

عنوان ژورنال:
  • Organic letters

دوره 12 3  شماره 

صفحات  -

تاریخ انتشار 2010