A Bifunctional B,N-Based Asymmetric Catalytic Nitrostyrene-Michael Addition Acting through a 10-Membered Ring Cyclic Transition State

Du Y., Sari O., ERDEM S., Whiting A.

HELVETICA CHIMICA ACTA, vol.104, no.12, 2021 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 104 Issue: 12
  • Publication Date: 2021
  • Doi Number: 10.1002/hlca.202100199
  • Journal Name: HELVETICA CHIMICA ACTA
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Aquatic Science & Fisheries Abstracts (ASFA), Biotechnology Research Abstracts, CAB Abstracts, Chemical Abstracts Core, Chimica, Compendex, EMBASE, Veterinary Science Database, DIALNET
  • Keywords: amino-boronic acid, asymmetric synthesis, B, N-bifunctional catalysis, homoboroproline, Michael addition, nitroalkenes, HIGHLY ENANTIOSELECTIVE SYNTHESIS, ORGANOBORON COMPOUNDS, DENSITY FUNCTIONALS, ACID, AMINE, ORGANOCATALYSTS, BORYLATION, MECHANISM, KETONES, DERIVATIVES
  • Marmara University Affiliated: Yes

Abstract

The B,N-bifunctional catalyst homoboroproline has been applied to a catalytic asymmetric nitroalkene-Michael addition to beta-nitrostyrene analogues, showing broad substrate tolerance, high conversions and moderate to good asymmetric induction. The ability of homoboroproline to act as an efficient catalyst based on enamine-formation of the secondary amine, coupled with intramolecular Lewis-acid chelation of the nitro function, in a non-FLP manner, to effect efficient and enantioselective catalysis via a proposed large 10-membered ring transition state is remarkable and reinforced by theoretical calculations.