Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 10, Issue 21, Pages 5443-5459Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200400443
Keywords
asymmetric synthesis; cyclopentenones; natural products; Pauson-Khand reactions; vinyl sulfoxides
Categories
Ask authors/readers for more resources
The use of sulfoxides as chiral auxiliaries in asymmetric intermolecular Pauson-Khand reactions is described. After screening a wide variety of substituents on the sulfur atom in alpha,beta-unsaturated sulfoxides, the readily available o-(N,N-dimethylamino)phenyl vinyl sulfoxide (1i) has proved to be highly reactive with substituted terminal alkynes under N-oxide-promoted conditions (CH3CN, 0degreesC). In addition, these Pauson-Khand reactions occurred with complete regioselectivity and very high diastereoselectivity (de = 86- >96%, (SRs) diastereomer). Experimental studies suggest that the high reactivity exhibited by the vinyl sulfoxide 1i relies on the ability of the amine group to act as a soft ligand on the alkyne dicobalt complex prior to the generation of the cobaltacycle intermediate. On the other hand, both theoretical and experimental studies show that the high stereoselectivity of the process is due to the easy thermodynamic epimerization at the C-5 center in the resulting 5-sulfinyl-2-cyclopentenone adducts. When it is taken into account that the known asymmetric intermolecular Pauson-Khand reactions are limited to the use of highly reactive bicyclic alkenes, mainly norbornene and norbornadiene, this novel procedure constitutes the first asymmetric version with unstrained acyclic alkenes. As a demonstration of the synthetic interest of this sulfoxide-based methodology in the enantioselective preparation of stereochemically complex cyclopentanoids, we have developed very short and efficient syntheses of the antibiotic (-)-pentenomycin I and the (-)-aminocyclopentitol moiety of a hopane triterpenoid.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available