Tributyltin hydride-mediated radical cyclisation of carbonyls to form functionalised oxygen and nitrogen heterocycles

J  Bentley; P A  Nilsson; A F  Parsons

doi:10.1039/b202077g

Tributyltin hydride-mediated radical cyclisation of carbonyls to form functionalised oxygen and nitrogen heterocycles

J Bentley, P A Nilsson, A F Parsons

Chemistry

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

Abstract

The tributyltin hydride-mediated cyclisation of unsaturated ethers and amines bearing an aldehyde or alpha,beta-unsaturated ketone group is reported. Cyclisation proceeds via reversible addition of the tributyltin radical to the carbonyl double bond to form an intermediate O-stannyl ketyl. This nucleophilic radical can add intramolecularly to electron-rich double bonds to form substituted 5- or 6-membered rings. The efficiency of the cyclisation to form, for example, hydroxytetrahydrofurans, chromanols or quinolones, is shown to depend on the nature of the acceptor double bond and also on the stability of the intermediate O-stannyl ketyl. Thus, resonance-stabilised allylic or benzylic O-stannyl ketyl radicals have been shown, for the first time, to have a particular application in slow radical cyclisations leading to butyrolactones or pyrans.

Original language	English
Pages (from-to)	1461-1469
Number of pages	9
Journal	Journal of the Chemical Society-Perkin Transactions 1
Issue number	12
DOIs	https://doi.org/10.1039/b202077g
Publication status	Published - 2002

Keywords

O-STANNYL KETYLS
CYCLIZATION REACTIONS
RING-CLOSURE
HYDROXY PYRROLIDINES
ALDEHYDES
KETONES
ESTERS
ROUTE
PIPERIDINES
DERIVATIVES

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10.1039/b202077g

Cite this

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title = "Tributyltin hydride-mediated radical cyclisation of carbonyls to form functionalised oxygen and nitrogen heterocycles",

abstract = "The tributyltin hydride-mediated cyclisation of unsaturated ethers and amines bearing an aldehyde or alpha,beta-unsaturated ketone group is reported. Cyclisation proceeds via reversible addition of the tributyltin radical to the carbonyl double bond to form an intermediate O-stannyl ketyl. This nucleophilic radical can add intramolecularly to electron-rich double bonds to form substituted 5- or 6-membered rings. The efficiency of the cyclisation to form, for example, hydroxytetrahydrofurans, chromanols or quinolones, is shown to depend on the nature of the acceptor double bond and also on the stability of the intermediate O-stannyl ketyl. Thus, resonance-stabilised allylic or benzylic O-stannyl ketyl radicals have been shown, for the first time, to have a particular application in slow radical cyclisations leading to butyrolactones or pyrans.",

keywords = "O-STANNYL KETYLS, CYCLIZATION REACTIONS, RING-CLOSURE, HYDROXY PYRROLIDINES, ALDEHYDES, KETONES, ESTERS, ROUTE, PIPERIDINES, DERIVATIVES",

author = "J Bentley and Nilsson, {P A} and Parsons, {A F}",

year = "2002",

doi = "10.1039/b202077g",

language = "English",

pages = "1461--1469",

journal = "Journal of the Chemical Society-Perkin Transactions 1",

issn = "0300-922X",

publisher = "Chemical Society",

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TY - JOUR

T1 - Tributyltin hydride-mediated radical cyclisation of carbonyls to form functionalised oxygen and nitrogen heterocycles

AU - Bentley, J

AU - Nilsson, P A

AU - Parsons, A F

PY - 2002

Y1 - 2002

N2 - The tributyltin hydride-mediated cyclisation of unsaturated ethers and amines bearing an aldehyde or alpha,beta-unsaturated ketone group is reported. Cyclisation proceeds via reversible addition of the tributyltin radical to the carbonyl double bond to form an intermediate O-stannyl ketyl. This nucleophilic radical can add intramolecularly to electron-rich double bonds to form substituted 5- or 6-membered rings. The efficiency of the cyclisation to form, for example, hydroxytetrahydrofurans, chromanols or quinolones, is shown to depend on the nature of the acceptor double bond and also on the stability of the intermediate O-stannyl ketyl. Thus, resonance-stabilised allylic or benzylic O-stannyl ketyl radicals have been shown, for the first time, to have a particular application in slow radical cyclisations leading to butyrolactones or pyrans.

AB - The tributyltin hydride-mediated cyclisation of unsaturated ethers and amines bearing an aldehyde or alpha,beta-unsaturated ketone group is reported. Cyclisation proceeds via reversible addition of the tributyltin radical to the carbonyl double bond to form an intermediate O-stannyl ketyl. This nucleophilic radical can add intramolecularly to electron-rich double bonds to form substituted 5- or 6-membered rings. The efficiency of the cyclisation to form, for example, hydroxytetrahydrofurans, chromanols or quinolones, is shown to depend on the nature of the acceptor double bond and also on the stability of the intermediate O-stannyl ketyl. Thus, resonance-stabilised allylic or benzylic O-stannyl ketyl radicals have been shown, for the first time, to have a particular application in slow radical cyclisations leading to butyrolactones or pyrans.

KW - O-STANNYL KETYLS

KW - CYCLIZATION REACTIONS

KW - RING-CLOSURE

KW - HYDROXY PYRROLIDINES

KW - ALDEHYDES

KW - KETONES

KW - ESTERS

KW - ROUTE

KW - PIPERIDINES

KW - DERIVATIVES

U2 - 10.1039/b202077g

DO - 10.1039/b202077g

M3 - Article

SN - 0300-922X

SP - 1461

EP - 1469

JO - Journal of the Chemical Society-Perkin Transactions 1

JF - Journal of the Chemical Society-Perkin Transactions 1

IS - 12

ER -