Enantioselective Organocatalysis and Superacid Activation: Challenges and Opportunities

Abstract

Since the pioneer reports of the groups of Akiyama and Terada on Brønsted acid organocatalysis, this field never stopped growing with the development of ingenious strategies for the activation of challenging poorly reactive substrates. The development of superacidic organocatalysts is an important way to selectively functionalize reluctant electrophiles and other approaches have also emerged such as the combination of Lewis and Brønsted acids as well as the consecutive organocatalysis and superacid activation. This Concept aims to highlight these different strategies and demonstrate their complementarity.

Accumulation, Characterization and Reactivity of Chiral Ammonium‐Carboxonium Dications in Superacid

“…9 : 1). While these data open interesting synthetic perspectives by exploiting this strategy, [33] they also awaken our curiosity at the mechanistic level. In order to get more insights behind the enhanced diastereoselectivity observed for proline aminoesters when compared to other aminoacids (i.e.…”

Organoselenium-Catalyzed C2,3-Diarylation of N–H Indoles

“…13 C{ 1 H}-NMR (151 MHz, CDCl 3 ) δ: 161. 2, 160.0, 159.1, 159.0, 136.7, 130.1, 127.4, 122.1, 121.9, 114.4, 113.5, 108.6, 106.7, 104.7, 90.9, 90.8, 55.7, 55.6, 55.4 2,4,. White solid (66.0 mg, 56% yield), mp: 177−179 °C; 1 H NMR (600 MHz, CDCl 3 ) δ: 8.77 (s, 1H), 7.71 (s, 1H), 7.36 (d,J = 8.4 Hz,1H),1H), 6.17 (s, 2H), 6.11 (s, 2H), 3.84 (s, 3H), 3.82 (s, 3H), 3.55 (s, 6H), 3.53 (s, 6H).…”

“…1 The groundbreaking contributions of MacMillan and List to small molecule asymmetrical organocatalysis were recognized with the prestigious Nobel Prize in Chemistry in 2021. 2 Organocatalysis distinguishes itself from metal catalysis by operating without the need for metals, employing mild reaction conditions, utilizing novel modes of activation, and demonstrating exceptional structural flexibility and adaptability. 3 Within the realm of organocatalysis, organoselenium catalysis has emerged as a particularly thriving area of investigation.…”