Synthesis of indolocarbazoles, bisindoles and related sulfur containing systems
Author: Janosik, Tomasz
Date: 2002-02-18
Location: Sal BI264, BiPontus, Södertörns Högskola, Huddinge
Time: 10.00
Department: Biovetenskaper och näringslära / Biosciences and Nutrition
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thesis.pdf (730.4Kb)
Abstract
This thesis is focussed mainly on the synthesis and reactions of various
indolocarbazoles, bisindoles and related sulfur containing systems, all
possessing structural features present in many biologically active,
natural or synthetic compounds.
In the first part, synthetic routes towards the planar, pentacyclic ring
systems of indolo[2,3-c]earbazole and indolo[3,2-a]carbazole are
described. The synthesis of the parent indolo[2,3-c]lcarbazole was
accomplished via a palladium acetate mediated cyclization of
1,2bis(1H-indol-2yl)ethane which was also demonstrated to serve as an
excellent precursor for the preparation of a variety -of cyclohept[1,2-b:5,4-b´]bisindoles
A variety of indolo[3,2a]carbazoles were obtained conveniently starting
from 2,3'-biindolyl via electrocyclic reactions, or the interaction of
2,3´-biindolyl with a masked N,N- dimethylaminoacetaldehyde. In an
extension, it was shown that access to indolo[3,2- a]pyrrolo[3,4-c]carbazoles
and analogues thereof can also be easily gained.
The second part of this thesis deals with the synthesis of the marine
alkaloid hyrtiosin B, which was achieved utilizing an efficient and
concise route involving acylation of indolozinc reagents derived from 5
-methoxyindole, or even better, 5-benzyloxyindole, as the key step.
In the final and major section, the chemistry and reactions of various
sulfur containing indoles and bisindoles are discussed. Thionation
reactions using elemental sulfur or P4S10 performed on e.g., indigo,
isatin, or 3,3'-biindolyl were shown to give bisindoles featuring
polysulfur bridges, or having unusual rings incorporating both sulfur and
phosphorus. The first example of a thionated indigo derivative with an
established structure, i.e. monothioindigo was isolated from the reaction
of indigo with P4S10 in pyridine. The interaction of sulfur with
2,2´-biindolyl was found to produce a system with four indole moieties
having a 12-membered central ring incorporating two S,S-linkages. This
molecule was also demonstrated to undergo transformation into two
different conformers on dissolution in warm strongly polar solvents. In
addition, the elusive [1,2]dithiino[4,3-b:5,6-b']diindole was isolated as
a N,N- dimethylacetamide solvate, the structure of which was rigorously
confirmed by X-ray crystallography Moreover, the synthesis and reactions
of pentathiepino[6,7-b]indoles were studied. Pentathiepino[6,7-b]indoles
proved to be readily accessible via the reaction of 2-lithiated indoles
with elemental sulfur. A modification of the conditions, ie. using of one
equivalent of sulfur, permitted a simple route to indoline-2 thiones from
indoles. In addition trimerization reactions of indoline-2-thione or
oxindole were investigated, demonstrating that treatment of
indoline-2-thione with p- toluenesulflanyl azide gives a cyclic trimeric
product while the oxidation of oxindole with iodine produces an acyclic
trimer.
List of papers:
I. Bergman J, Janosik T, Yudina L, Desarbre E, Lidgren G, Venemalm L (2000). "Reactions of 1,2-bis(1H-indol-2-yl)ethane: formation of indolo [2,3-c]carbazole and cyclohept[1,2-b:5,4-b]bisindole derivatives." Tetrahedron 56: 1911
II. Janosik T, Bergman J (1999). "Reactions of 2,3-biindolyl: synthesis of indolo[3,2-a]carbazoles." Tetrahedron 55: 2371
III. Bergaman J, Janosik T, Johnsson AL (1999). "Synthesis of hyrtiosin B, a bisindole alkaloid from the Okinawan marine sponge Hyrtios erecta." Synthesis 580
IV. Janosik T, Bergman J, Stensland B, stalhandske C (2002). "Thionation of bisindole derivatives with P4S10 or elemental sulfur." J Chem Soc Perkin Trans (In Print)
V. Janosik T, Bergman J, Romero I, Stensland B, Stalhandske C, Marques MMB, Santos MMM, Lobo AM, Prabhakar S, duarte MF, Florencio MH (2002). "Synthetic, spectroscopic, and X-ray crystallographic studies of [1,2,7,8]tetrathiacyclododecino[4,3-b:5,6-b:10,9-b:11,12-b]tetraindoles." (Submitted)
VI. Rewcastle GW, Janosik T, Bergman J (2001). "Reactions of 2-lithiated indoles with elemental sulfur. Formation of pentathiepino[6,7-b]indoles and indoline-2-thiones." Tetrahedron 57: 7185
VII. Janosik T, Bergman J (2002). "Oxidative coupling of indoline-2-thione or oxindole: formation of cyclic and acyclic indole trimers." (Manuscript)
I. Bergman J, Janosik T, Yudina L, Desarbre E, Lidgren G, Venemalm L (2000). "Reactions of 1,2-bis(1H-indol-2-yl)ethane: formation of indolo [2,3-c]carbazole and cyclohept[1,2-b:5,4-b]bisindole derivatives." Tetrahedron 56: 1911
II. Janosik T, Bergman J (1999). "Reactions of 2,3-biindolyl: synthesis of indolo[3,2-a]carbazoles." Tetrahedron 55: 2371
III. Bergaman J, Janosik T, Johnsson AL (1999). "Synthesis of hyrtiosin B, a bisindole alkaloid from the Okinawan marine sponge Hyrtios erecta." Synthesis 580
IV. Janosik T, Bergman J, Stensland B, stalhandske C (2002). "Thionation of bisindole derivatives with P4S10 or elemental sulfur." J Chem Soc Perkin Trans (In Print)
V. Janosik T, Bergman J, Romero I, Stensland B, Stalhandske C, Marques MMB, Santos MMM, Lobo AM, Prabhakar S, duarte MF, Florencio MH (2002). "Synthetic, spectroscopic, and X-ray crystallographic studies of [1,2,7,8]tetrathiacyclododecino[4,3-b:5,6-b:10,9-b:11,12-b]tetraindoles." (Submitted)
VI. Rewcastle GW, Janosik T, Bergman J (2001). "Reactions of 2-lithiated indoles with elemental sulfur. Formation of pentathiepino[6,7-b]indoles and indoline-2-thiones." Tetrahedron 57: 7185
VII. Janosik T, Bergman J (2002). "Oxidative coupling of indoline-2-thione or oxindole: formation of cyclic and acyclic indole trimers." (Manuscript)
Issue date: 2002-01-28
Rights:
Publication year: 2002
ISBN: 91-7349-110-1
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