Change search
ReferencesLink to record
Permanent link

Direct link
Enantioselective Platinum-Catalyzed Silicon-Boron Addition to 1,3-Cyclohexadiene
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0002-1743-7650
2005 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 347, no 6, 749-753 p.Article in journal (Refereed) Published
Abstract [en]

Silaboration of 1,3-cyclohexadiene in the presence of Pt(acac)(2), DIBALH, and a phosphoramidite prepared from (S)-1,1'-bi-2-naphthol and diisopropylamine led to (1R,4S)-1-(dimethylphenylsilyl)4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene with 70% ee. Chiral catalysts based on Ni gave no or essentially racemic product, whereas complexes containing Pd were inactive.





Place, publisher, year, edition, pages
Weinheim: Wiley-VCH , 2005. Vol. 347, no 6, 749-753 p.
Keyword [en]
asymmetric catalysis; dienes; enantioselective; platinum; silaboration
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-9389DOI: 10.1002/adsc.200505016ISI: 000229345400003ScopusID: 2-s2.0-20044378514OAI: diva2:113836
QC 20100727Available from: 2008-11-03 Created: 2008-10-30 Last updated: 2010-07-27Bibliographically approved
In thesis
1. Silaborations of Unsaturated Compounds
Open this publication in new window or tab >>Silaborations of Unsaturated Compounds
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis deals with the development of transition metal-catalyzed silaborations of 1,3-dienes and 1,6-enynes.

The first part of the thesis describes the development of the enantioselective 1,4-silaboration of 1,3-cyclohexadiene. A number of chiral metal-ligand complexes were evaluated. Up to 82% enantiomeric excess was obtained using a catalyst system derived from Pt(acac)2 and a phosphoramidite ligand. The product formed was employed in allylborations of aldehydes, giving homo-allylic alcohols in good yields with good to moderate diastereoselectivity. In attempts to widen the scope of silaborations to include acyclic, terminally substituted 1,3-dienes, products from H-B exchange with, and H-Si addition to, the dienes were obtained.

The second part describes the development of silaborative carbocyclization of 1,6-enynes. A Pd N-heterocylic carbene complex was found to be effective for the silaborative carbocyclization of unsubstituted enynes, giving the products in good to excellent yields. Employing terminally substituted enynes resulted in low or no yields.

The last part describes investigations into the reaction mechanisms of the processes developed in the first part. It was found that the silylborane undergoes oxidative addition to a Pt(0) complex generated from Pt(acac)2 and DIBALH. After insertion of 1,3-cyclohexadiene into the Pt-B bond a π-allyl complex was observed experimentally. In the addition of silylborane to acyclic, terminally substituted, 1,3-dienes it was shown by deuterium labeling experiments that one diene loses a hydride via H-B exchange and that this hydride is then added to another diene via H-Si addition. A reaction mechanism was proposed for this process.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 53 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2008:67
allylboration, bismetallation, boron, carbocyclization, catalysis, 1, 3-diene, enantioselective, 1, 6-enyne, interelement, N-heterocyclic carbene, nickel, palladium, phosphine, phosphoramidite, platinum, reaction mechanism, silaboration, silicon, silylborane, stereoselective
National Category
Other Basic Medicine
urn:nbn:se:kth:diva-9440 (URN)978-91-7415-151-0 (ISBN)
Public defence
2008-11-21, D2, KTH, Lindstedtsvägen 5, Stockholm, 10:15 (Swedish)
QC 20100924Available from: 2008-11-04 Created: 2008-11-04 Last updated: 2010-09-24Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Gerdin, MartinMoberg, Christina
By organisation
Organic Chemistry
In the same journal
Advanced Synthesis and Catalysis
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 45 hits
ReferencesLink to record
Permanent link

Direct link