Diastereoselective Petasis‐Borono‐Mannich Crotylation Reactions of Chiral α‐Heteroatom (F, OBz, OH) Aldehydes: Rapid Access to Valuable Mono and Bicyclic Heterocyclic Scaffolds
Abstract: The crotylation reactions of chiral α‐F, α‐OBz and α‐OH aldehydes under Petasis‐borono‐Mannich conditions using (E)‐ or (Z)‐crotylboronates and primary amines resulted in γ‐addition products in high dr and high er. α‐F and α‐OBz aldehydes gave 1,2‐anti‐2,3‐syn and 1,2‐anti‐2,3‐anti, products, respectively while an α‐OH aldehyde gave 1,2‐syn‐2,3‐syn products. The stereochemical outcomes of reactions of the former aldehydes can be explained using a six‐membered ring transition state (TS) model in which a Cornforth‐like conformation around the imine intermediate is favoured resulting in 1,2‐anti products. The 2,3‐stereochemical outcome is dependent upon the geometry of the crotylboronate. These TS models were also supported by DFT calculations. The stereochemical outcomes of reactions employing an α‐OH aldehyde can be rationalised as occurring via an open‐TS involving H‐bonding in the imine intermediate between the α‐OH group and the imine N atom. Representative products were converted to highly functionalized 1,2,3,6‐tetrahydropyridines and 3H‐oxazolo[3,4‐a]pyridine‐3‐ones which will be valuable scaffolds in synthesis.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Diastereoselective Petasis‐Borono‐Mannich Crotylation Reactions of Chiral α‐Heteroatom (F, OBz, OH) Aldehydes: Rapid Access to Valuable Mono and Bicyclic Heterocyclic Scaffolds ; day:17 ; month:08 ; year:2023 ; extent:13
Chemistry - a European journal ; (17.08.2023) (gesamt 13)
- Creator
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Chevis, Philip J.
Chao, Chi Bong Eric
Richardson, Christopher
Hyland, Christopher
Lee, Richmond
Pyne, Stephen G.
- DOI
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10.1002/chem.202301701
- URN
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urn:nbn:de:101:1-2023081815145810967824
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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14.08.2025, 10:46 AM CEST
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Associated
- Chevis, Philip J.
- Chao, Chi Bong Eric
- Richardson, Christopher
- Hyland, Christopher
- Lee, Richmond
- Pyne, Stephen G.
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