Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation
Heterocycle-derived aldehydes are challenging substrates in metal-catalysed hydroacylation chemistry. We show that by using azine N-oxide substituted aldehydes, good reactivity can be achieved, and that they are highly effective substrates for the intermolecular hydroacylation of alkynes. Employing...
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | English |
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Royal Society of Chemistry
2021
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| _version_ | 1826307562246504448 |
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| author | Moseley, DF Kalepu, J Willis, MC |
| author_facet | Moseley, DF Kalepu, J Willis, MC |
| author_sort | Moseley, DF |
| collection | OXFORD |
| description | Heterocycle-derived aldehydes are challenging substrates in metal-catalysed hydroacylation chemistry. We show that by using azine N-oxide substituted aldehydes, good reactivity can be achieved, and that they are highly effective substrates for the intermolecular hydroacylation of alkynes. Employing a Rh(I)-catalyst, we achieve a mild and scalable aldehyde C–H activation, that permits the coupling with unactivated terminal alkynes, in good yields and with high regioselectivities (up to >20 : 1 l:b). Both substrates can tolerate a broad variety of functional groups. The reaction can also be applied to diazine aldehydes that contain a free N-lone pair. We demonstrate conversion of the hydroacylation products to the corresponding azine, through a one-pot hydroacylation/deoxygenation sequence. A one-pot hydroacylation/cyclisation, using N-Boc propargylamine, additionally leads to the synthesis of a bidentate pyrrolyl ligand. |
| first_indexed | 2024-03-07T07:04:58Z |
| format | Journal article |
| id | oxford-uuid:941e9b51-38ff-4a79-b426-b083d1bf1992 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:04:58Z |
| publishDate | 2021 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:941e9b51-38ff-4a79-b426-b083d1bf19922022-04-29T09:58:54ZAzine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:941e9b51-38ff-4a79-b426-b083d1bf1992EnglishSymplectic ElementsRoyal Society of Chemistry2021Moseley, DFKalepu, JWillis, MCHeterocycle-derived aldehydes are challenging substrates in metal-catalysed hydroacylation chemistry. We show that by using azine N-oxide substituted aldehydes, good reactivity can be achieved, and that they are highly effective substrates for the intermolecular hydroacylation of alkynes. Employing a Rh(I)-catalyst, we achieve a mild and scalable aldehyde C–H activation, that permits the coupling with unactivated terminal alkynes, in good yields and with high regioselectivities (up to >20 : 1 l:b). Both substrates can tolerate a broad variety of functional groups. The reaction can also be applied to diazine aldehydes that contain a free N-lone pair. We demonstrate conversion of the hydroacylation products to the corresponding azine, through a one-pot hydroacylation/deoxygenation sequence. A one-pot hydroacylation/cyclisation, using N-Boc propargylamine, additionally leads to the synthesis of a bidentate pyrrolyl ligand. |
| spellingShingle | Moseley, DF Kalepu, J Willis, MC Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title | Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title_full | Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title_fullStr | Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title_full_unstemmed | Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title_short | Azine N-oxides as effective controlling groups for Rh-catalysed intermolecular alkyne hydroacylation |
| title_sort | azine n oxides as effective controlling groups for rh catalysed intermolecular alkyne hydroacylation |
| work_keys_str_mv | AT moseleydf azinenoxidesaseffectivecontrollinggroupsforrhcatalysedintermolecularalkynehydroacylation AT kalepuj azinenoxidesaseffectivecontrollinggroupsforrhcatalysedintermolecularalkynehydroacylation AT willismc azinenoxidesaseffectivecontrollinggroupsforrhcatalysedintermolecularalkynehydroacylation |