TMEDA-assisted effective direct ortho arylation of electron-deficient N-heteroarenes with aromatic Grignard reagents.

نویسندگان

  • Fang-Fang Zhuo
  • Wen-Wen Xie
  • Yong-Xin Yang
  • Lei Zhang
  • Pei Wang
  • Rui Yuan
  • Chao-Shan Da
چکیده

In the addition of TMEDA in toluene, aryl Grignards could effectively and site-specifically ortho-arylate electron-deficient heteroarenes under mild conditions. This endeavor successfully changed the old low-yielding reaction, aryl Grignard addition to N-heteroarenes, into an efficient procedure for heterobiaryls. The combination of the inexpensive aryl Grignards, TMEDA, the cost-free air, no use of any transition-metal catalyst, the mild reaction conditions, and the high-yielding gram-scale results enables this new procedure to be cost-effective and potentially utilizable in industry.

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

Direct α-arylation of ethers through the combination of photoredox-mediated C-H functionalization and the Minisci reaction.

The direct α-arylation of cyclic and acyclic ethers with heteroarenes has been accomplished through the design of a photoredox-mediated CH functionalization pathway. Transiently generated α-oxyalkyl radicals, produced from a variety of widely available ethers through hydrogen atom transfer (HAT), were coupled with a range of electron-deficient heteroarenes in a Minisci-type mechanism. This mil...

متن کامل

Palladium-Catalyzed Direct Arylation of 5-Halouracils and 5-Halouracil Nucleosides with Arenes and Heteroarenes Promoted by TBAF

The 1-N-benzyl-5-iodo(or bromo)uracil undergoes Pd-catalyzed [Pd2(dba)3] direct arylation with benzene and other simple arenes in the presence of TBAF in DMF without the necessity of adding any ligands or additives to give 5-arylated uracil analogues. The TBAF-promoted coupling also occurs efficiently with electron rich heteroarenes at 100 °C (1 h) even with only small excess of heteroarenes. T...

متن کامل

N-Heterocyclic carbene–palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides

New Pd-NHC complexes have been synthesized and employed for palladium-catalyzed direct arylation of pyrrole derivatives by using electron-deficient aryl chlorides as coupling partners. The desired coupling products were obtained in moderate to good yields by using 1 mol % of these air-stable palladium complexes. This is an advantage compared to the procedures employing air-sensitive phosphines,...

متن کامل

Pd-catalyzed N-arylation of secondary acyclic amides: catalyst development, scope, and computational study.

We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, and chlorides. This method allows for easy variation of the aromatic component in tertiary aryl amides. A new biaryl phosphine with P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective for this amidation. The critical aspects of the ligand were ex...

متن کامل

Copper-free arylation of 3,3-disubstituted allylic halides with triazene-softened aryl Grignard reagents.

A copper-free allylic arylation reaction between 3,3-disubstituted allylic halides and triazene-softened aryl Grignard reagents has been developed. This protocol presents a direct and efficient way to construct both α- or γ-isomers with high regioselectivity under environmentally benign conditions. Various functional groups can be tolerated in the reaction and the products are of high value for...

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:
  • The Journal of organic chemistry

دوره 78 7  شماره 

صفحات  -

تاریخ انتشار 2013