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...

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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
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container_issue 18
container_start_page 3027
container_title Chemical communications (Cambridge, England)
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creator Sahari, Aleksi
Cuong Dat Do
Mannisto, Jere K
Antico, Emanuele
Amaratunga, Angelo
Hopmann, Kathrin H
Repo, Timo
description 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.
doi_str_mv 10.1039/d2cc00446a
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source NORA - Norwegian Open Research Archives; Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list)
subjects Aldehydes
Benzaldehyde
Butyrolactone
Carbon dioxide
Lactones
Magnesium chloride
Reagents
Stereoselectivity
Substitutes
Titanium
title Titanium isopropoxide-mediated cis-selective synthesis of 3,4-substituted butyrolactones from CO2
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