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New chiral I+ complexes for "reagent"-controlled reactions : a combined computational and synthetic approach

Haas, Jürgen. New chiral I+ complexes for "reagent"-controlled reactions : a combined computational and synthetic approach. 2003, Doctoral Thesis, University of Basel, Faculty of Science.

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Official URL: http://edoc.unibas.ch/diss/DissB_6853

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Abstract

Amines are known to form strong complexes with ICl, their potential in organic synthesis is therefore of
high interest. Thus chiral complexes with enantiomerically pure amines were investigated by synthetic,
spectroscopical and computational means. The complex formed between (R)-1-phenyl-ethylamineA and ICl has been investigated in NMR titrations,
which showed the formation of a 1:1 complex and indicated subsequent transformations. These compounds
have been investigated experimentally and also have been described by quantum chemical investigations.
Furthermore with the aid of ab initio and DFT calculations a chiral complex C, formed by B and ICl could be identi�ed. The charge transfer complex C between (R)-1,2,3,4-tetrahydro-1-naphthylamine B and ICl
resembles a chiral electrophile and after a proton-iodine exchange the N-iodo species D is formed. This is
supported by time-dependent UV/VIS studies and also NMR titration experiments. If the reaction between
B and ICl is continued for two hours, followed by an aequeous workup, the formation of �-tetralone was
observed, which is also strongly supporting the conversion of C to D.
In the iodolactonisation reaction of 4-phenyl-4-pentenoic acid E to 5-iodomethyl-5-phenyl-dihydrofuran-2-one F, an enantiomeric excess (ee) of 45% was observed. This result was obtained after stirring B and
ICl for 30 minutes, bevor the actual lactonisation was performed at
Advisors:Giese, Bernd
Committee Members:Wirth, T. and Woggon, Wolf-Dietrich
Faculties and Departments:05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Bioorganische Chemie (Giese)
UniBasel Contributors:Haas, Jürgen and Giese, Bernd and Woggon, Wolf-Dietrich
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:6853
Thesis status:Complete
Bibsysno:Link to catalogue
Number of Pages:95
Language:English
Identification Number:
Last Modified:22 Apr 2018 04:30
Deposited On:13 Feb 2009 14:55

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