Titanium isopropoxide-mediated cis-selective synthesis of 3,4-substituted butyrolactones from CO2

We report a Ti(OiPr)4-mediated multicomponent reaction, which produces 3,4-substituted cis-δ-lactones from alkyl magnesium chloride, benzaldehyde and CO2. The key intermediate, titanacyclopropane, is formed in situ from Ti(OiPr)4 and a Grignard reagent, which enables 1,2-dinucleophilic reactivity th...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Chemical communications (Cambridge, England) England), 2022-03, Vol.58 (18), p.3027-3030
Hauptverfasser: Sahari, Aleksi, Cuong Dat Do, Mannisto, Jere K, Antico, Emanuele, Amaratunga, Angelo, Hopmann, Kathrin H, Repo, Timo
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:We report a Ti(OiPr)4-mediated multicomponent reaction, which produces 3,4-substituted cis-δ-lactones from alkyl magnesium chloride, benzaldehyde and CO2. The key intermediate, titanacyclopropane, is formed in situ from Ti(OiPr)4 and a Grignard reagent, which enables 1,2-dinucleophilic reactivity that is used to insert carbon dioxide and an aldehyde. An alternative reaction route is also described where a primary alkene is used to create the titanacyclopropane. A computational analysis of the elementary steps shows that the carbon dioxide and the aldehyde insertion proceeds through an inner-sphere mechanism. A variety of cis-butyrolactones can be synthesized with up to 7 : 1 diastereoselectivity and 77% yield.
ISSN:1359-7345
1364-548X
1364-548X
DOI:10.1039/d2cc00446a