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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
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
ISBN
91-628-5368-6
language
English
LU publication?
yes
id
8948a837-b4ec-44d0-bdf5-8eaf6115f5c8 (old id 465234)
date added to LUP
2007-10-14 15:28:13
date last changed
2016-09-19 08:45:02
@misc{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},
  keyword      = {Organic chemistry,Organisk kemi,non-covalent bonds.,molecular recognition,desymmetrization,metal-mediated reactions,Tröger's base,synthetic protocols},
  language     = {eng},
  pages        = {61},
  publisher    = {ARRAY(0xb6ccbe0)},
  title        = {General Protocols for the Preparation of Tröger's Base Analogues and Molecular Recognition by Designed Tröger's Base Receptors},
  year         = {2002},
}