Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Nucleophile dependent formation of 6- and 7-membered N-heterocycles by platinum-catalysed cyclisation of 1,5-bisallenes
AU - Quirós, María Teresa
AU - Hurtado-Rodrigo, César
AU - Muñoz, María Paz
PY - 2017/7/31
Y1 - 2017/7/31
N2 - An unprecedented Pt-catalysed cyclisation of N-tethered 1,5-bisallenes in the presence of oxygen nucleophiles is reported, where formation of 6- or 7-membered rings is driven by the choice of nucleophile and the mechanism dictated by the nucleophile and the electronic properties of the bisallene. The reaction in the presence of alcohols gives preferentially vinyltetrahydropyridines with an extra alkoxy group and Pt-H as the active species in the catalytic cycle, while formation of di- and tetrahydroazepines with an extra hydroxyl group is favoured when water is used as nucleophile, via nucleophilic attack/carbocyclization as the favoured pathway. The products obtained are frequently found in the core of natural products with important biological activities, so understanding this complex mechanistic behaviour and exploiting this new methodology will have a big impact in organic synthesis and organometallic chemistry.
AB - An unprecedented Pt-catalysed cyclisation of N-tethered 1,5-bisallenes in the presence of oxygen nucleophiles is reported, where formation of 6- or 7-membered rings is driven by the choice of nucleophile and the mechanism dictated by the nucleophile and the electronic properties of the bisallene. The reaction in the presence of alcohols gives preferentially vinyltetrahydropyridines with an extra alkoxy group and Pt-H as the active species in the catalytic cycle, while formation of di- and tetrahydroazepines with an extra hydroxyl group is favoured when water is used as nucleophile, via nucleophilic attack/carbocyclization as the favoured pathway. The products obtained are frequently found in the core of natural products with important biological activities, so understanding this complex mechanistic behaviour and exploiting this new methodology will have a big impact in organic synthesis and organometallic chemistry.
KW - mechanisms
KW - catalysis
KW - platinum
KW - allenes
U2 - 10.1039/C7OB01469D
DO - 10.1039/C7OB01469D
M3 - Journal article
VL - 15
SP - 6731
EP - 6737
JO - Organic and Biomolecular Chemistry
JF - Organic and Biomolecular Chemistry
SN - 1477-0520
IS - 32
ER -