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New approach to biomimetic transamination using bifunctional [1,3]-proton transfer catalysis in thioxanthenyl dioxide imines.

Hjelmencrantz, Anders and Berg, Ulf LU (2002) In Journal of Organic Chemistry 67(11). p.3585-3594
Abstract
A pyridoxamine equivalent, 9-aminothioxanthene 10,10-dioxide, has been designed that is capable of affording transamination in good to excellent yields of natural as well as artificial amino acids. Amidines and guanidines in catalytic amounts were capable of performing [1,3]-proton transfer in the imines under mild conditions, whereas various simple amines failed. The use of chiral catalysts resulted in modest asymmetric induction (ee </= 45%). The electronic dependence in para-substituted phenyl glyoxylate imines, isotope effects, and computational studies support a stepwise, bifunctional mechanism for amidine and guanidine catalysts. Attempts toward an autocatalytic model system are described.
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Organic Chemistry
volume
67
issue
11
pages
3585 - 3594
publisher
The American Chemical Society
external identifiers
  • pmid:12027668
  • wos:000175915000006
  • scopus:0037204686
ISSN
1520-6904
DOI
10.1021/jo0106748
language
English
LU publication?
yes
id
a0c74ef9-717e-4841-9502-e83ee6b20daa (old id 108500)
date added to LUP
2007-07-10 11:02:48
date last changed
2017-02-26 03:40:22
@article{a0c74ef9-717e-4841-9502-e83ee6b20daa,
  abstract     = {A pyridoxamine equivalent, 9-aminothioxanthene 10,10-dioxide, has been designed that is capable of affording transamination in good to excellent yields of natural as well as artificial amino acids. Amidines and guanidines in catalytic amounts were capable of performing [1,3]-proton transfer in the imines under mild conditions, whereas various simple amines failed. The use of chiral catalysts resulted in modest asymmetric induction (ee &lt;/= 45%). The electronic dependence in para-substituted phenyl glyoxylate imines, isotope effects, and computational studies support a stepwise, bifunctional mechanism for amidine and guanidine catalysts. Attempts toward an autocatalytic model system are described.},
  author       = {Hjelmencrantz, Anders and Berg, Ulf},
  issn         = {1520-6904},
  language     = {eng},
  number       = {11},
  pages        = {3585--3594},
  publisher    = {The American Chemical Society},
  series       = {Journal of Organic Chemistry},
  title        = {New approach to biomimetic transamination using bifunctional [1,3]-proton transfer catalysis in thioxanthenyl dioxide imines.},
  url          = {http://dx.doi.org/10.1021/jo0106748},
  volume       = {67},
  year         = {2002},
}