Formal nucleophilic pyrrolylmethylation via palladium-based auto-tandem catalysis: switchable regiodivergent synthesis and remote chirality transfer.
Chem Sci
; 13(42): 12433-12439, 2022 Nov 02.
Article
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| MEDLINE
| ID: mdl-36349271
ABSTRACT
Although nucleophilic benzylation-type reaction to introduce various aromatic systems into molecules has been widely explored, the related pyrrolylmethylation version remains to be disclosed. Reported herein is a palladium-catalysed multiple auto-tandem reaction between N-Ts propargylamines, allyl carbonates and aldimines in the presence of an acid, proceeding through sequential allylic amination, cycloisomerisation, vinylogous addition and aromatisation steps. A diversity of formal pyrrolylmethylated amine products were finally furnished efficiently. In addition, switchable regiodivergent 3-pyrrolylmethylation and 4-pyrrolylmethylation were realised by tuning catalytic conditions. Moreover, remote chirality transfer with readily available enantioenriched starting materials was well achieved with an achiral ligand, relying on diastereoselective generation of η2-Pd(0) complexes between Pd(0) and chiral 1,3-diene intermediates in the key vinylogous addition step. A few control experiments were conducted to elucidate the palladium-involved tandem reaction and regiodivergent synthesis.
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01-internacional
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MEDLINE
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En
Revista:
Chem Sci
Año:
2022
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Article