Prevalence of Diarylprolinol Silyl Ethers as Catalysts in Total Synthesis and Patents

Abstract

Diarylprolinol silyl ethers are among the most utilized stereoselective organocatalysts for the construction of complex molecules. With their debut in 2005, these catalysts have been applied in numerous method developments primarily leveraging enamine and iminium-ion catalysis. These strategies have extended into the preparation of complex molecules in both academic and industrial settings. This Review intends to give an overview of the application of the diarylprolinol silyl ether catalysts in total synthesis. Furthermore, integration of these catalysts in patent literature is also disclosed highlighting the versatility of the catalytic system.

Mapping the Surface Groups of Amine-Rich Carbon Dots Enables Covalent Catalysis in Aqueous Media

“…Building on the extensive characterization of the amino-rich CDs domains, we envisioned the use of NCDs-1 as water-soluble catalysts tackling the activation of aldehydes and ketones, which are both expected to occur vis-a `-vis the structural diversity of the reactive amine groups identified by 19 F-NMR. [53][54][55][56][57][58][59] Indeed, the iminium-ion species detected by in situ NMR analysis are the electrophilic catalytic intermediates responsible for the LUMO-lowering activation in aminocatalysis, able to engage in conjugate addition with a series of nucleophiles. [60][61][62] To this aim, we first evaluated the reactivity between p-F-cinnamaldehyde (1a) and N-methylindole (3a) as biologically relevant Cnucleophile.…”

Advances in Chiral Metal–Organic and Covalent Organic Frameworks for Asymmetric Catalysis

“…Because of its extensive sources and easy modification, proline and its derivatives, mainly 2-substituted chiral pyrrolidines, have been widely used in asymmetric organic synthesis. [45] Incorporation of prolinederived chiral units into MOFs, generating efficient heterogeneous asymmetric organocatalysts, has attracted significant interest in the past decade. A great many of proline-based MOF organocatalysts have been explored by introduction of chiral units into frameworks via either postsynthetic modification or direct synthesis (always in a N-protected form).…”

Advances in the Asymmetric Total Synthesis of Natural Products Using Chiral Secondary Amine Catalyzed Reactions of α,β-Unsaturated Aldehydes

“…Over the past eighteen years, iminium ion activation strategy has extended into the synthesis of complex molecules including natural products and pharmaceuticals. Given the importance of the chiral secondary amines catalysts it is no doubt there have been a lot of reviews on organocatalysis [8,9,10,11,12,13,14]. But the relatively complete review on the total synthesis of natural products and relevant drugs published from 2002 to 2018 by using the strategy of chiral secondary amines catalyzed reactions of α,β-unsaturated aldehydes is still necessary.…”