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

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

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.

• Jezik: Angleški jezik
• Ključne besede: (+)-camphor, diamines, thiourea, bifunctional organocatalysts, asymmetric synthesis
• Vrsta gradiva: Članek v reviji
• Tipologija: 1.01 - Izvirni znanstveni članek
• Organizacija: FKKT - Fakulteta za kemijo in kemijsko tehnologijo
• Status publikacije: Objavljeno
• Različica publikacije: Objavljena publikacija
• Leto izida: 2020
• Št. strani: 22 str.
• Številčenje: Vol. 25, iss. 13, art. 2978
• PID: 20.500.12556/RUL-133821
• UDK: 547.415.1
• ISSN pri članku: 1420-3049
• DOI: 10.3390/molecules25132978
• COBISS.SI-ID: 24479491
• Datum objave v RUL: 16.12.2021

Gradivo je del revije

• Naslov: Molecules
• Skrajšan naslov: Molecules
• Založnik: MDPI
• ISSN: 1420-3049
• COBISS.SI-ID: 18462981

Licence

• Licenca: CC BY 4.0, Creative Commons Priznanje avtorstva 4.0 Mednarodna
• Povezava: http://creativecommons.org/licenses/by/4.0/deed.sl
• Opis: To je standardna licenca Creative Commons, ki daje uporabnikom največ možnosti za nadaljnjo uporabo dela, pri čemer morajo navesti avtorja.
• Začetek licenciranja: 01.07.2020

Sekundarni jezik

• Jezik: Slovenski jezik
• Ključne besede: (+)-kafra, diamini, tiosečnina, bifunkcionalni organokatalizatorji, asimetrična sinteza

Projekti

• Financer: ARRS - Agencija za raziskovalno dejavnost Republike Slovenije
• Številka projekta: P1-0179
• Naslov: Napredna organska sinteza in kataliza

• Financer: ARRS - Agencija za raziskovalno dejavnost Republike Slovenije
• Številka projekta: P1-0175
• Naslov: Napredna anorganska kemija