Consecutive oxygen-based oxidations convert amines to α-cyanoepoxides.

نویسندگان

  • Dmitry B Ushakov
  • Kerry Gilmore
  • Peter H Seeberger
چکیده

Tri- or tetrasubstituted α-cyanoepoxides can be rapidly prepared from unactivated amines and malononitrile or methyl cyanoacetate when singlet oxygen, produced in a continuous-flow photoreactor, serves as an oxidant and in situ peroxide source. The hydrogen peroxide generated in amine oxidation epoxidizes an electron deficient olefin intermediate, formed by deaminative Mannich coupling. The corresponding α,α-dicyano- or α-cyano-α-esterepoxides were obtained in good yields (43-82%).

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

Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold–titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Fu...

متن کامل

Generation of reactive species and fate of thiols during peroxidase-catalyzed metabolic activation of aromatic amines and phenols.

The horseradish peroxidase (HRP)-catalyzed oxidation of p-phenetidine and acetaminophen was investigated. Studies using the spin probe 2-ethyl-1-hydroxy-2,5,5-trimethyl-3-oxazolidine (OXANOH) suggested these oxidations involve the generation of substrate-derived free radicals. This was confirmed by using glutathione (GSH) in these incubations in the presence of the spin trap 5,5-dimethyl-1-pyrr...

متن کامل

Developments in Synthetic Application of Selenium(IV) Oxide and Organoselenium Compounds as Oxygen Donors and Oxygen-Transfer Agents.

A variety of selenium compounds were proven to be useful reagents and catalysts for organic synthesis over the past several decades. The most interesting aspect, which emerged in recent years, concerns application of hydroperoxide/selenium(IV) oxide and hydroperoxide/organoselenium catalyst systems, as "green reagents" for the oxidation of different organic functional groups. The topic of oxida...

متن کامل

Copper-catalyzed aerobic oxidative synthesis of α-ketoamides from methyl ketones, amines and NIS at room temperature.

A simple, efficient and practical copper-catalyzed aerobic oxidative synthesis of α-ketoamides from aryl methyl ketones, aliphatic amines and N-iodosuccinimide (NIS) has been developed. The one-pot reaction may proceed smoothly at room temperature in the open air. The possible mechanism for the formation of α-ketoamides was proposed. Molecular oxygen in air functions as both an oxidant and an o...

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:
  • Chemical communications

دوره 50 84  شماره 

صفحات  -

تاریخ انتشار 2014