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Definitions of ligands (see also Figure 3): Dpe-phos = bis[2-(diphenylphosphino)phenyl] ether; Xantphos = 9,9-dimethyl-4,5- bis(diphenylphosphino)-xanthene; NiXantphos = 4,6-bis(diphenylphosphino)- phenoxazine; dppe = 1,2-bis(diphenylphosphino)ethane; dppp = 1,3-bis(diphenylphosphino)propane; dppb = 1,4-bis-(diphenylphosphino)butane.
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Definitions of ligands (see also Figure 3): Dpe-phos = bis[2-(diphenylphosphino)phenyl] ether; Xantphos = 9,9-dimethyl-4,5- bis(diphenylphosphino)-xanthene; NiXantphos = 4,6-bis(diphenylphosphino)- phenoxazine; dppe = 1,2-bis(diphenylphosphino)ethane; dppp = 1,3-bis(diphenylphosphino)propane; dppb = 1,4-bis-(diphenylphosphino)butane.
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A small amount of a regioisomer analogous to 18 was also formed in this reaction.
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A small amount of a regioisomer analogous to 18 was also formed in this reaction.
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Surprisingly, the stereochemical outcome of the piperazine-forming reactions is opposite to that predicted by the allylic strain model, similar to that shown in Scheme 11. Our current working hypothesis suggests that the piperazine-forming reactions proceed through a transition state in which the N-aryl group is rotated to minimize allylic strain interactions, and the structure around the cyclizing nitrogen atom is pyramidal. Investigations into this hypothesis are currently underway.
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Surprisingly, the stereochemical outcome of the piperazine-forming reactions is opposite to that predicted by the allylic strain model, similar to that shown in Scheme 11. Our current working hypothesis suggests that the piperazine-forming reactions proceed through a transition state in which the N-aryl group is rotated to minimize allylic strain interactions, and the structure around the cyclizing nitrogen atom is pyramidal. Investigations into this hypothesis are currently underway.
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