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Diastereoselective Aldol reaction of Zincated 3-Chloro-3-methyl-1-azaallylic anions as key step in the synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines

Sven Mangelinckx UGent, Bart De Sterck UGent, Filip Colpaert UGent, Saron Catak UGent, Jan Jacobs UGent, Stijn Rooryck, Michel Waroquier UGent, Veronique Van Speybroeck UGent and Norbert De Kimpe UGent (2012) JOURNAL OF ORGANIC CHEMISTRY. 77(7). p.3415-3425
abstract
Zincated 3-chloro-3-methyl-1-azaallylic anions undergo a stereoselective aldol addition across aromatic aldehydes and subsequent mesylation to produce syn alpha-chloro-beta-mesyloxyketimines, which were isolated in 80-84% yield and high diastereomeric excess (dr > 97/3) after purification via flash chromatography. The syn alpha-chloro-beta-mesyloxyketimines were further stereoselectively reduced to give stereochemically defined 3-aminopropyl mesylates, which were cyclized to 1,2,3,4-tetrasubstituted 3-chloroazetidines containing three contiguous stereogenic centers. DFT calculations on the key aldol addition revealed the presence of a highly ordered bimetallic six-membered twist-boat-like transition state structure with a tetra-coordinated metal cyclic structure. DFT calculations revealed that chelation of both zinc and lithium cations in the transition state structure leads to the experimentally observed high syn diastereoselectivity of aldol reactions.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
3-HALO-1-AZAALLYLIC ANIONS, THEORETICAL RATIONALIZATION, RING-OPENING REACTIONS, STEREOSELECTIVE-SYNTHESIS, 1, 3-ASYMMETRIC INDUCTION, HETEROCYCLIC CHEMISTRY, CONVENIENT SYNTHESIS, ASYMMETRIC-SYNTHESIS, ADDITION-REACTIONS, ORGANIC-CHEMISTRY
journal title
JOURNAL OF ORGANIC CHEMISTRY
J. Org. Chem.
volume
77
issue
7
pages
3415 - 3425
Web of Science type
Article
Web of Science id
000302388000041
JCR category
CHEMISTRY, ORGANIC
JCR impact factor
4.564 (2012)
JCR rank
9/55 (2012)
JCR quartile
1 (2012)
ISSN
0022-3263
DOI
10.1021/jo300203t
language
English
UGent publication?
yes
classification
A1
additional info
Stijn Rooryck zou tot Department of Sustainable Organic Chemistry and Technology moeten behoren, maar lijkt niet voor te komen in de database.
copyright statement
I have transferred the copyright for this publication to the publisher
id
2094885
handle
http://hdl.handle.net/1854/LU-2094885
date created
2012-04-26 11:38:24
date last changed
2013-04-06 00:30:37
@article{2094885,
  abstract     = {Zincated 3-chloro-3-methyl-1-azaallylic anions undergo a stereoselective aldol addition across aromatic aldehydes and subsequent mesylation to produce syn alpha-chloro-beta-mesyloxyketimines, which were isolated in 80-84\% yield and high diastereomeric excess (dr {\textrangle} 97/3) after purification via flash chromatography. The syn alpha-chloro-beta-mesyloxyketimines were further stereoselectively reduced to give stereochemically defined 3-aminopropyl mesylates, which were cyclized to 1,2,3,4-tetrasubstituted 3-chloroazetidines containing three contiguous stereogenic centers. DFT calculations on the key aldol addition revealed the presence of a highly ordered bimetallic six-membered twist-boat-like transition state structure with a tetra-coordinated metal cyclic structure. DFT calculations revealed that chelation of both zinc and lithium cations in the transition state structure leads to the experimentally observed high syn diastereoselectivity of aldol reactions.},
  author       = {Mangelinckx, Sven and De Sterck, Bart and Colpaert, Filip and Catak, Saron and Jacobs, Jan and Rooryck, Stijn and Waroquier, Michel and Van Speybroeck, Veronique and De Kimpe, Norbert},
  issn         = {0022-3263},
  journal      = {JOURNAL OF ORGANIC CHEMISTRY},
  keyword      = {3-HALO-1-AZAALLYLIC ANIONS,THEORETICAL RATIONALIZATION,RING-OPENING REACTIONS,STEREOSELECTIVE-SYNTHESIS,1,3-ASYMMETRIC INDUCTION,HETEROCYCLIC CHEMISTRY,CONVENIENT SYNTHESIS,ASYMMETRIC-SYNTHESIS,ADDITION-REACTIONS,ORGANIC-CHEMISTRY},
  language     = {eng},
  number       = {7},
  pages        = {3415--3425},
  title        = {Diastereoselective Aldol reaction of Zincated 3-Chloro-3-methyl-1-azaallylic anions as key step in the synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines},
  url          = {http://dx.doi.org/10.1021/jo300203t},
  volume       = {77},
  year         = {2012},
}

Chicago
Mangelinckx, Sven, Bart De Sterck, Filip Colpaert, Saron Catak, Jan Jacobs, Stijn Rooryck, Michel Waroquier, Veronique Van Speybroeck, and Norbert De Kimpe. 2012. “Diastereoselective Aldol Reaction of Zincated 3-Chloro-3-methyl-1-azaallylic Anions as Key Step in the Synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines.” Journal of Organic Chemistry 77 (7): 3415–3425.
APA
Mangelinckx, S., De Sterck, B., Colpaert, F., Catak, S., Jacobs, J., Rooryck, S., Waroquier, M., et al. (2012). Diastereoselective Aldol reaction of Zincated 3-Chloro-3-methyl-1-azaallylic anions as key step in the synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines. JOURNAL OF ORGANIC CHEMISTRY, 77(7), 3415–3425.
Vancouver
1.
Mangelinckx S, De Sterck B, Colpaert F, Catak S, Jacobs J, Rooryck S, et al. Diastereoselective Aldol reaction of Zincated 3-Chloro-3-methyl-1-azaallylic anions as key step in the synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines. JOURNAL OF ORGANIC CHEMISTRY. 2012;77(7):3415–25.
MLA
Mangelinckx, Sven, Bart De Sterck, Filip Colpaert, et al. “Diastereoselective Aldol Reaction of Zincated 3-Chloro-3-methyl-1-azaallylic Anions as Key Step in the Synthesis of 1,2,3,4-Tetrasubstituted 3-Chloroazetidines.” JOURNAL OF ORGANIC CHEMISTRY 77.7 (2012): 3415–3425. Print.