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...

Full description

Saved in:
Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2022-03, Vol.58 (18), p.3027-3030
Main Authors: Sahari, Aleksi, Cuong Dat Do, Mannisto, Jere K, Antico, Emanuele, Amaratunga, Angelo, Hopmann, Kathrin H, Repo, Timo
Format: Article
Language:English
Subjects:
Aldehydes
Benzaldehyde
Butyrolactone
Carbon dioxide
Lactones
Magnesium chloride
Reagents
Stereoselectivity
Substitutes
Titanium
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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