Pi-allyl-metal intermediates in organic synthesis
Pi-allyl-metal intermediates in organic synthesis
The palladium(O) catalysed reaction of butadiene and phenylhydrazones to yield either azo or N-butenyl and N-octadienyl phenylhydrazone adducts has been investigated. Whilst formation of the azo derivatives is favoured in the presence of Pd(PPh)4, exclusive formation of the latter products is observed for the PdC12-PPh3 catalyzed reaction. Methylhydrazones were also shown to react with butadiene in. the presence of Pd(PPh3)4 to selectively yield N-octa-2,7-dien-l-yl derivatives in high yield. The Pd(PPh3)4 catalyzed reaction of butadiene and benzaldehyde and acetophenone ximaa yielded both butenyl and octadienyl oxime ether adducts i.i high yield. Aliphatic oximes and butadiene only reacted in the presence of either Pd(NO3)2-PPh3 or Pd(acac)2-P(OPh)3 toyield octadienyl oxime ethers and an isoxazolidine derivative, however, and the latter is the exclusive product for the reaction of aldehyde oximes. Butadiene and dimethylhydrazonee, oximes, oxime ethers, pyridine -N-oxide and nitrones failed to react in the presence of various palladium(O) catalysts.The reaction of rt-allylnickel bromides with organonitrogen compounds has also been investigated. Whilst rf-(2-carbethoxy) allylnickel bromide and amines reacted to give oC-methylene- y -lactam derivatives in fair yield, rt-allylnickel bromide only reacted with propionaldehyde amine to give 2-ethyl 4,5-dimethyl pyridine in 19% yield. No reactions were observed between the former complex and hydrazones, oximes, oxime ethers and 1,3 dipolar reagents. The application of the coupling reactions of these complexes and halides to the synthesis of macrolides has also been initiated, and the synthesis of the dibromide precursorto Z-dec-4-en-9-olide is given.
University of Southampton
1978
Nobbs, Malcom Stuart
(1978)
Pi-allyl-metal intermediates in organic synthesis.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The palladium(O) catalysed reaction of butadiene and phenylhydrazones to yield either azo or N-butenyl and N-octadienyl phenylhydrazone adducts has been investigated. Whilst formation of the azo derivatives is favoured in the presence of Pd(PPh)4, exclusive formation of the latter products is observed for the PdC12-PPh3 catalyzed reaction. Methylhydrazones were also shown to react with butadiene in. the presence of Pd(PPh3)4 to selectively yield N-octa-2,7-dien-l-yl derivatives in high yield. The Pd(PPh3)4 catalyzed reaction of butadiene and benzaldehyde and acetophenone ximaa yielded both butenyl and octadienyl oxime ether adducts i.i high yield. Aliphatic oximes and butadiene only reacted in the presence of either Pd(NO3)2-PPh3 or Pd(acac)2-P(OPh)3 toyield octadienyl oxime ethers and an isoxazolidine derivative, however, and the latter is the exclusive product for the reaction of aldehyde oximes. Butadiene and dimethylhydrazonee, oximes, oxime ethers, pyridine -N-oxide and nitrones failed to react in the presence of various palladium(O) catalysts.The reaction of rt-allylnickel bromides with organonitrogen compounds has also been investigated. Whilst rf-(2-carbethoxy) allylnickel bromide and amines reacted to give oC-methylene- y -lactam derivatives in fair yield, rt-allylnickel bromide only reacted with propionaldehyde amine to give 2-ethyl 4,5-dimethyl pyridine in 19% yield. No reactions were observed between the former complex and hydrazones, oximes, oxime ethers and 1,3 dipolar reagents. The application of the coupling reactions of these complexes and halides to the synthesis of macrolides has also been initiated, and the synthesis of the dibromide precursorto Z-dec-4-en-9-olide is given.
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Published date: 1978
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Local EPrints ID: 458464
URI: http://eprints.soton.ac.uk/id/eprint/458464
PURE UUID: 811c282e-085c-4026-9bcc-3e5c82f66a83
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Date deposited: 04 Jul 2022 16:49
Last modified: 04 Jul 2022 16:49
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Author:
Malcom Stuart Nobbs
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