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General Protocols for the Preparation of Tröger's Base Analogues and Molecular Recognition by Designed Tröger's Base Receptors

Jensen, Jacob LU (2002)
Abstract
2,8-Dihalo substituted analogues of Tröger’s base were prepared via the Tröger’s base condensation reaction. These compounds were used as synthetic intermediates for the preparation of otherwise inaccessible functionalized Tröger’s base analogues.



Based on 2,8-diiodo-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine, a mild room temperature protocol for the introduction of terminal functionalized alkynes into the Tröger’s base core via Sonogashira reaction was developed.



Efficient double and single bromine-lithium exchanges of 2,8-dibromo-6H,12H-5,11-methanodibenzo[b,f]- [1,5]diazocine afforded C2-symmetric and asymmetric analogues respectively. The desymmetrization procedure allowed for the... (More)
2,8-Dihalo substituted analogues of Tröger’s base were prepared via the Tröger’s base condensation reaction. These compounds were used as synthetic intermediates for the preparation of otherwise inaccessible functionalized Tröger’s base analogues.



Based on 2,8-diiodo-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine, a mild room temperature protocol for the introduction of terminal functionalized alkynes into the Tröger’s base core via Sonogashira reaction was developed.



Efficient double and single bromine-lithium exchanges of 2,8-dibromo-6H,12H-5,11-methanodibenzo[b,f]- [1,5]diazocine afforded C2-symmetric and asymmetric analogues respectively. The desymmetrization procedure allowed for the sequential introduction of two different electrophiles.



Using the 2,8-dihalo substituted analogues of Tröger’s base as aryl halides, as well as precursors of organometallic species, allowed for the synthesis of novel analogues via cross-coupling reactions.



Association constants of terminal bisammonium salts with a bis(crown-ether) Tröger’s base receptor were increased by exploiting solvophobic interactions with the Tröger’s base in it’s cavity, and CH-Pi and Pi-Pi -interactions with the benzo groups. (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Wilcox, Craig S.
organization
publishing date
type
Thesis
publication status
published
subject
keywords
Organic chemistry, Organisk kemi, non-covalent bonds., molecular recognition, desymmetrization, metal-mediated reactions, Tröger's base, synthetic protocols
pages
61 pages
publisher
Organic Chemistry, Lund University
defense location
Chemical Center, Hall B
defense date
2002-12-14 10:15:00
ISBN
91-628-5368-6
language
English
LU publication?
yes
additional info
Article: I. Jensen, J. and Wärnmark, K. Synthesis 2001, 1873-77. Synthesis of Halogen Substituted Analogues of Tröger’s Base. Article: II. Jensen, J.; Strozyk, M. and Wärnmark, K. submitted, Influence of Scale, Stoichiometry and Temperature on the Synthesis of 2,8-Dihalo Analogues of Tröger’s Base from the Corresponding Anilines and Paraformaldehyde. Article: III. Jensen, J.; Strozyk, M. and Wärnmark, K. Synthesis, 2002, in press. Introduction of Terminal Alkynes into the 2- and 8-Positions of the Tröger’s Base Core via Sonogashira Reaction of 4,10-Dimethyl-2,8-diiodo-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine. Article: IV. Jensen, J.; Tejler, J. and Wärnmark, K. J. Org. Chem. 2002, 67, 6008-6014. General Protocols for the Synthesis of C2-Symmetric and Asymmetric 2,8-Disubstituted Analogues of Tröger’s Base via Efficient Bromine-Lithium Exchanges of 2,8-Dibromo-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine. Article: V. Jensen, J.; Olomi, Z. and Wärnmark, K. in manuscript. Introduction of Aromatic and Heteroaromatic Groups into the 2- and 8-Positions of the Tröger’s Base Core via Suzuki Cross-Coupling of 6H,12H-5,11-Methanodibenzo[b,f][1,5]diazocine-2,8-diboronic Ester. Article: VI. Jensen, J.; Norrby, P.-O.; Dawaigher, S.; Mauro, N.; Hansson A. P. and Wärnmark, K. in manuscript. Selectivity in the Recognition of 4-Substituted Heptane-1,7-diyl Bisammonium Salts with a Bis(Crown-Ether) Analogue of Tröger’s Base. Solvophobic Effects and p-Interactions of the Tröger’s Base Core. The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
id
8948a837-b4ec-44d0-bdf5-8eaf6115f5c8 (old id 465234)
date added to LUP
2016-04-04 10:07:06
date last changed
2018-11-21 20:56:51
@phdthesis{8948a837-b4ec-44d0-bdf5-8eaf6115f5c8,
  abstract     = {2,8-Dihalo substituted analogues of Tröger’s base were prepared via the Tröger’s base condensation reaction. These compounds were used as synthetic intermediates for the preparation of otherwise inaccessible functionalized Tröger’s base analogues.<br/><br>
<br/><br>
Based on 2,8-diiodo-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine, a mild room temperature protocol for the introduction of terminal functionalized alkynes into the Tröger’s base core via Sonogashira reaction was developed.<br/><br>
<br/><br>
Efficient double and single bromine-lithium exchanges of 2,8-dibromo-6H,12H-5,11-methanodibenzo[b,f]- [1,5]diazocine afforded C2-symmetric and asymmetric analogues respectively. The desymmetrization procedure allowed for the sequential introduction of two different electrophiles.<br/><br>
<br/><br>
Using the 2,8-dihalo substituted analogues of Tröger’s base as aryl halides, as well as precursors of organometallic species, allowed for the synthesis of novel analogues via cross-coupling reactions.<br/><br>
<br/><br>
Association constants of terminal bisammonium salts with a bis(crown-ether) Tröger’s base receptor were increased by exploiting solvophobic interactions with the Tröger’s base in it’s cavity, and CH-Pi and Pi-Pi -interactions with the benzo groups.},
  author       = {Jensen, Jacob},
  isbn         = {91-628-5368-6},
  language     = {eng},
  publisher    = {Organic Chemistry, Lund University},
  school       = {Lund University},
  title        = {General Protocols for the Preparation of Tröger's Base Analogues and Molecular Recognition by Designed Tröger's Base Receptors},
  year         = {2002},
}