Regiospecific reductive elimination from diaryliodonium salts.

نویسندگان

  • Bijia Wang
  • Joseph W Graskemper
  • Linlin Qin
  • Stephen G DiMagno
چکیده

StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) is provided by the cyclophane substituent on iodine(III). Computational and experimental studies demonstrate that out of plane steric bulk strongly destabilizes the reductive elimination transition state, and leads to regiochemical control. This approach should be general for high valent main group and transition metal ions.

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

Unprecedented directing group ability of cyclophanes in arene fluorinations with diaryliodonium salts.

For the first time it is shown that exceptionally electron-rich arene rings can be fluorinated exclusively during the reductive elimination reactions of diaryliodonium fluorides. The 5-methoxy[2.2]paracyclophan-4-yl directing group simultaneously reduces unproductive aryne chemistry and eliminates ligand exchange reactions by a combination of steric and electronic effects. Use of the cyclophane...

متن کامل

Synthesis of quaternary aryl phosphonium salts: photoredox-mediated phosphine arylation.

We report a synthesis method for the construction of quaternary aryl phoshonium salts at ambient temperature. The regiospecific reaction involves the coupling of phosphines with aryl radicals derived from diaryliodonium salts under photoredox conditions.

متن کامل

Sterically Congested 2,6‐Disubstituted Anilines from Direct C−N Bond Formation at an Iodine(III) Center

2,6-Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(I...

متن کامل

Mechanistic Investigations of Cu-Catalyzed Fluorination of Diaryliodonium Salts: Elaborating the CuI/CuIII Manifold in Copper Catalysis

A combination of experimental and density functional theory (DFT) investigations suggests that the Cu-catalyzed fluorination of unsymmetrical diaryliodonium salts with general structure [Mes(Ar)I]+ in N,N'-dimethylformamide proceeds through a CuI/CuIII catalytic cycle. A low concentration of fluoride relative to combined iodonium reagent plus copper ensures that [Mes(Ar)I]+ is available as the ...

متن کامل

Thiophosphoramides as cooperative catalysts for copper-catalyzed arylation of carboxylates with diaryliodonium salts.

A thiophosphoramide-based co-catalyst was found to significantly accelerate copper(II) trifluoromethanesulfonate-catalyzed arylation of potassium carboxylates with diaryliodonium salts. This effect could be attributed to counterion activation of diaryliodonium salts or organocopper intermediates by thiophosphoramides. Inclusion of thiophosphoramides permits achieving significantly milder reacti...

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 49 24  شماره 

صفحات  -

تاریخ انتشار 2010