A general synthesis of unnatural α-amino acids by iron-catalysed olefin-olefin coupling: Via generated radicals

Herein, we report an efficient and practical protocol for the asymmetric synthesis of unnatural α-amino acids (AAs) with γ-tertiary and quaternary carbon centres via selective intermolecular iron-catalysed olefin-olefin coupling of a chiral Ni(ii) complex of dehydroalanine Schiff base 2 ((S)-BPB-Ni-Δ-Ala) with different olefins. In all successful reactions, diastereomeric nickel complexes were typically obtained in a ratio of up to dr > 20:1. The desired products were isolated in 42-93% yields (18 examples). Exemplarily, the three Ni(ii) complexes obtained were decomposed with aqueous HCl and the target unnatural α-amino acids were isolated with excellent enantioselectivities and yields of up to 83%. The chiral auxiliary (BPB = 2-(N-benzylprolyl)aminobenzophenone) was readily recycled and reused for the synthesis of the starting chiral Ni(ii) complex 2. The developed protocol provided a facile access to the analogues of glutamic acid, leucine and phosphinothricin. © the Partner Organisations 2019.

Авторы
Larionov V.A. 1, 2 , Stoletova N.V.1 , Kovalev V.I.3 , Smol'Yakov A.F. 1, 4 , Savel'Yeva T.F.1 , Maleev V.I. 1
Издательство
Royal Society of Chemistry
Номер выпуска
8
Язык
Английский
Страницы
1094-1099
Статус
Опубликовано
Том
6
Год
2019
Организации
  • 1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str. 28, Moscow, 119991, Russian Federation
  • 2 Department of Inorganic Chemistry, Peoples' Friendship University of Russia, RUDN University, Miklukho-Maklaya Str. 6, Moscow, 117198, Russian Federation
  • 3 Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow, 125047, Russian Federation
  • 4 Plekhanov Russian University of Economics, Stremyanny per. 36, Moscow, 117997, Russian Federation
Ключевые слова
Amino acids; Catalysis; Chlorine compounds; Iron; Olefins; Alpha-amino acids; Aminobenzophenone; Asymmetric synthesis; Chiral auxiliaries; Dehydroalanine; Nickel complex; Phosphinothricin; Quaternary carbon; Nickel compounds
Дата создания
19.07.2019
Дата изменения
19.07.2019
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/38493/
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