Microwave-assisted [2 + 3] cycloaddition of nitrones to platinum-(II) and -(IV) bound organonitriles

M. Adília Januário Charmier; Vadim Yu Kukushkin; Armando J.L. Pombeiro

doi:10.1039/b301892j

Microwave-assisted [2 + 3] cycloaddition of nitrones to platinum-(II) and -(IV) bound organonitriles

M. Adília Januário Charmier, Vadim Yu Kukushkin, Armando J.L. Pombeiro

Research output: Contribution to journal › Article › peer-review

41 Citations (Scopus)

Abstract

The coordinated EtCN in the anionic platinum(II) [Ph₃PCH ₂Ph][PtCl₃(EtCN)], the neutral platinum(II) [PtCl ₂(EtCN)₂] or the neutral platinum(IV) [PtCl ₄(EtCN)₂] complexes undergo [2 + 3] cycloadditions with cyclic non-aromatic nitrones and these reactions are greatly accelerated by microwave irradiation, to give, with a high stereoselectivity, complexes with bicyclic fused oxadiazolines as a racemic mixture in 60-90% yields, while acyclic nitrones are much less reactive and give a mixture of two diastereoisomers in the ratio 1:1. The new bicyclic oxadiazoline ligands can be liberated by reaction with a diphosphine. However, with a cyclic aromatic nitrone no cycloaddition is observed and only the product of the nitrile substitution is obtained. All compounds were characterised by elemental analyses, IR ¹H, ¹³C and ¹⁹⁵Pt NMR spectroscopies.

Original language	English
Pages (from-to)	2540-2543
Number of pages	4
Journal	Dalton Transactions
Issue number	12
DOIs	https://doi.org/10.1039/b301892j
Publication status	Published - 21 Jun 2003

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title = "Microwave-assisted [2 + 3] cycloaddition of nitrones to platinum-(II) and -(IV) bound organonitriles",

abstract = "The coordinated EtCN in the anionic platinum(II) [Ph3PCH 2Ph][PtCl3(EtCN)], the neutral platinum(II) [PtCl 2(EtCN)2] or the neutral platinum(IV) [PtCl 4(EtCN)2] complexes undergo [2 + 3] cycloadditions with cyclic non-aromatic nitrones and these reactions are greatly accelerated by microwave irradiation, to give, with a high stereoselectivity, complexes with bicyclic fused oxadiazolines as a racemic mixture in 60-90% yields, while acyclic nitrones are much less reactive and give a mixture of two diastereoisomers in the ratio 1:1. The new bicyclic oxadiazoline ligands can be liberated by reaction with a diphosphine. However, with a cyclic aromatic nitrone no cycloaddition is observed and only the product of the nitrile substitution is obtained. All compounds were characterised by elemental analyses, IR 1H, 13C and 195Pt NMR spectroscopies.",

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year = "2003",

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doi = "10.1039/b301892j",

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journal = "Dalton Transactions",

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T1 - Microwave-assisted [2 + 3] cycloaddition of nitrones to platinum-(II) and -(IV) bound organonitriles

AU - Charmier, M. Adília Januário

AU - Kukushkin, Vadim Yu

AU - Pombeiro, Armando J.L.

PY - 2003/6/21

Y1 - 2003/6/21

N2 - The coordinated EtCN in the anionic platinum(II) [Ph3PCH 2Ph][PtCl3(EtCN)], the neutral platinum(II) [PtCl 2(EtCN)2] or the neutral platinum(IV) [PtCl 4(EtCN)2] complexes undergo [2 + 3] cycloadditions with cyclic non-aromatic nitrones and these reactions are greatly accelerated by microwave irradiation, to give, with a high stereoselectivity, complexes with bicyclic fused oxadiazolines as a racemic mixture in 60-90% yields, while acyclic nitrones are much less reactive and give a mixture of two diastereoisomers in the ratio 1:1. The new bicyclic oxadiazoline ligands can be liberated by reaction with a diphosphine. However, with a cyclic aromatic nitrone no cycloaddition is observed and only the product of the nitrile substitution is obtained. All compounds were characterised by elemental analyses, IR 1H, 13C and 195Pt NMR spectroscopies.

AB - The coordinated EtCN in the anionic platinum(II) [Ph3PCH 2Ph][PtCl3(EtCN)], the neutral platinum(II) [PtCl 2(EtCN)2] or the neutral platinum(IV) [PtCl 4(EtCN)2] complexes undergo [2 + 3] cycloadditions with cyclic non-aromatic nitrones and these reactions are greatly accelerated by microwave irradiation, to give, with a high stereoselectivity, complexes with bicyclic fused oxadiazolines as a racemic mixture in 60-90% yields, while acyclic nitrones are much less reactive and give a mixture of two diastereoisomers in the ratio 1:1. The new bicyclic oxadiazoline ligands can be liberated by reaction with a diphosphine. However, with a cyclic aromatic nitrone no cycloaddition is observed and only the product of the nitrile substitution is obtained. All compounds were characterised by elemental analyses, IR 1H, 13C and 195Pt NMR spectroscopies.

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DO - 10.1039/b301892j

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SN - 1477-9226

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JO - Dalton Transactions

JF - Dalton Transactions

IS - 12

ER -

Microwave-assisted [2 + 3] cycloaddition of nitrones to platinum-(II) and -(IV) bound organonitriles

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