Organomolybdenum Complexes in Organic Synthesis- New methods for the Preparation of Cationic Diene Complexes and Applications to Synthesis
(2002)- Abstract
- Indolyl substituted pyranyl- and cyclohexenyl molybdenum complexes were synthesised through stereoselective nucleophilic addition of indoles to the corresponding cationic 2H-pyran or cyclohexadiene molybdenum complex. Decomplexation of an allylic molybdneum complex by treatment with iodine gave 1-(4-iodo-2-cyclohexenyl)-1H-indole-3-carbonitrile in high regio-selectivity. A new method for preparation of eta-4-diene molybdneum complexes was developed based on in situ generation of carbenium ions effectuating hydride abstraction from neutral eta-3-allylic substrates. The presence of 1,1,1,3,3,3-hexafluoroisopropanol as a co-solvent was critical for successful hydride abstraction to occur with various di-or triarylmethyl halides or carbinols... (More)
- Indolyl substituted pyranyl- and cyclohexenyl molybdenum complexes were synthesised through stereoselective nucleophilic addition of indoles to the corresponding cationic 2H-pyran or cyclohexadiene molybdenum complex. Decomplexation of an allylic molybdneum complex by treatment with iodine gave 1-(4-iodo-2-cyclohexenyl)-1H-indole-3-carbonitrile in high regio-selectivity. A new method for preparation of eta-4-diene molybdneum complexes was developed based on in situ generation of carbenium ions effectuating hydride abstraction from neutral eta-3-allylic substrates. The presence of 1,1,1,3,3,3-hexafluoroisopropanol as a co-solvent was critical for successful hydride abstraction to occur with various di-or triarylmethyl halides or carbinols as carbenium ion precursors. The first enantioselective hydride abstraction from an allylic molybdenum complex was performed, with an enantiomeric excess of up to 10%, utilising non-racemic 1-alkoxy-9-hydroxyxanthene derivatives as carbenium ion precursors. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/464266
- author
- Bjurling, Emelie LU
- supervisor
- opponent
-
- Prof Moberg, Christina
- organization
- publishing date
- 2002
- type
- Thesis
- publication status
- published
- subject
- keywords
- Organisk kemi, Organic chemistry, indoles, carbenium ions, hexafluoroisopropanol, hydride abstraction, molybdenum, cationic diene complexes
- pages
- 106 pages
- publisher
- Organic Chemistry, Lund University
- defense location
- N/A
- defense date
- 2001-01-26 10:15:00
- ISBN
- 91-7874-172-6
- language
- English
- LU publication?
- yes
- additional info
- Article: Bjurling, E.; Johansson, M. H.; Andersson, C.-M.Synthesis of N-(2-Puranyl)-and N- Cyclohexenylindole Derivatives via StereoselectiveAddition of Indole Nucleophiles to Organomolybdneum Complexes.Organometallics, 1999, 18, 5606-5613. Article: Bjurling, E.; Andersson, C.-M.An alternative Procedure for Preparing Cationic eta-4-Diene- Molybdenum Complexesfrom the Corresponding Allylic Precursors.Tetrahedron Lett. 1999, 40, 1981. Article: Bjurling, E.; Björkman, A.; Andersson, C.-M.Preparation of Cationic Cyclopentadienyl Diene Molybdneum Complexes throughHydride Abstraction Effected by Di- or Triarylmethyl Halides in the Presence ofHexafluoro-2-propanol.Organometallics, 2001, 20, 990-994. Article: Bjurling E.; Berg, U.; Andersson, C.-M.Hydride Abstraction from eta-3-Allylic Molybdenum Complexes Exploring Various DiarylCarbenium Ion Precursors. A Study towards Enantioselective Hydride Abstraction.Submitted for publication. 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
- 09b840c9-cc60-465c-8722-790f8fb0a84a (old id 464266)
- date added to LUP
- 2016-04-04 11:24:07
- date last changed
- 2018-11-21 21:04:37
@phdthesis{09b840c9-cc60-465c-8722-790f8fb0a84a, abstract = {{Indolyl substituted pyranyl- and cyclohexenyl molybdenum complexes were synthesised through stereoselective nucleophilic addition of indoles to the corresponding cationic 2H-pyran or cyclohexadiene molybdenum complex. Decomplexation of an allylic molybdneum complex by treatment with iodine gave 1-(4-iodo-2-cyclohexenyl)-1H-indole-3-carbonitrile in high regio-selectivity. A new method for preparation of eta-4-diene molybdneum complexes was developed based on in situ generation of carbenium ions effectuating hydride abstraction from neutral eta-3-allylic substrates. The presence of 1,1,1,3,3,3-hexafluoroisopropanol as a co-solvent was critical for successful hydride abstraction to occur with various di-or triarylmethyl halides or carbinols as carbenium ion precursors. The first enantioselective hydride abstraction from an allylic molybdenum complex was performed, with an enantiomeric excess of up to 10%, utilising non-racemic 1-alkoxy-9-hydroxyxanthene derivatives as carbenium ion precursors.}}, author = {{Bjurling, Emelie}}, isbn = {{91-7874-172-6}}, keywords = {{Organisk kemi; Organic chemistry; indoles; carbenium ions; hexafluoroisopropanol; hydride abstraction; molybdenum; cationic diene complexes}}, language = {{eng}}, publisher = {{Organic Chemistry, Lund University}}, school = {{Lund University}}, title = {{Organomolybdenum Complexes in Organic Synthesis- New methods for the Preparation of Cationic Diene Complexes and Applications to Synthesis}}, year = {{2002}}, }