Stereodivergent synthesis of camphor-derived diamines and their application as thiourea organocatalysts

Ričko, Sebastijan (author), Požgan, Franc (author), Štefane, Bogdan (author), Svete, Jurij (author), Golobič, Amalija (author), Grošelj, Uroš (author)

A series of 18 regio- and stereo-chemically diverse chiral non-racemic 1,2-, 1,3-, and 1,4-diamines have been synthesized from commercial (1S)-(+)-ketopinic acid and (1S)-(+)-10-camphorsulfonic acid. The structures of the diamines are all based on the D-(+)-camphor scaffold and feature isomeric diversity in terms of regioisomeric attachment of the primary and the tertiary amine function and the exo/endo-isomerism. Diamines were transformed into the corresponding noncovalent bifunctional thiourea organocatalysts, which have been evaluated for catalytic activity in the conjugative addition of 1,3-dicarbonyl nucleophiles (dimethyl malonate, acetylacetone, and dibenzoylmethane) to trans-β-nitrostyrene. The highest enantioselectivity was achieved in the reaction with acetylacetone as nucleophile using endo-1,3-diamine derived catalyst 52 (91.5:8.5 er). All new organocatalysts 48–63 have been fully characterized. The structures and the absolute configurations of eight intermediates and thiourea derivative 52 were also determined by X-ray diffraction.

• Language: English
• Keywords: (+)-camphor, diamines, thiourea, bifunctional organocatalysts, asymmetric synthesis
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2020
• Number of pages: 22 str.
• Numbering: Vol. 25, iss. 13, art. 2978
• PID: 20.500.12556/RUL-133821
• UDC: 547.415.1
• ISSN on article: 1420-3049
• DOI: 10.3390/molecules25132978
• COBISS.SI-ID: 24479491
• Publication date in RUL: 16.12.2021

Record is a part of a journal

• Title: Molecules
• Shortened title: Molecules
• Publisher: MDPI
• ISSN: 1420-3049
• COBISS.SI-ID: 18462981

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.
• Licensing start date: 01.07.2020

Secondary language

• Language: Slovenian
• Keywords: (+)-kafra, diamini, tiosečnina, bifunkcionalni organokatalizatorji, asimetrična sinteza

Projects

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0179
• Name: Napredna organska sinteza in kataliza

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0175
• Name: Napredna anorganska kemija