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Highly Selective Hydroaminomethylation of Internal Alkenes To Give Linear Amines
Author(s) -
Ahmed Moballigh,
Bronger Raymond P. J.,
Jackstell Ralf,
Kamer Paul C. J.,
van Leeuwen Piet W. N. M.,
Beller Matthias
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600702
Subject(s) - hydroformylation , xantphos , chemistry , regioselectivity , isomerization , rhodium , amination , organic chemistry , catalysis , combinatorial chemistry , palladium
The application of phenoxaphosphino‐modified Xantphos‐type ligands ( 1 – 9 ) in the rhodium‐catalyzed hydroaminomethylation of internal olefins to give linear amines is reported. Excellent chemo‐ and regioselectivities have been obtained through the use of 0.1 mol % [Rh(cod) 2 ]BF 4 /0.4 mol % xantphenoxaphos ( 1 ), providing a practical and environmentally attractive synthetic route for the preparation of amines from internal alkenes. For the first time, both functionalized internal olefins and mixtures of internal and terminal olefins have been converted highly selectively into linear amines. Investigations of the effects of the calculated natural bite angles of ligands on hydroaminomethylation shows that the regioselectivity for the linear product follows a similar trend to that seen in the hydroformylation of internal alkenes with the aid of these ligands. Hydroaminomethylation and each of its individual steps were monitored by high‐pressure infrared spectroscopy. The results suggest that hydroaminomethylations take place by a sequential isomerization/hydroformylation/amination/hydrogenation pathway.