Catalytic, Efficient, and syn-Selective Construction of Deoxypolypropionates and Other Chiral Compounds via Zr-Catalyzed Asymmetric Carboalumination of Allyl Alcohol
- 7 February 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (9) , 2770-2771
- https://doi.org/10.1021/ja0530974
Abstract
An efficient, syn-selective, all catalytic asymmetric protocol for the synthesis of α,ω-diheterofunctional deoxypolypropionates via Zr-catalyzed asymmetric carboalumination (ZACA reaction) was developed. The success of the method critically hinges on the one-pot conversion of unprotected allyl alcohol into TBS-protected (R)- or (S)-3-iodo-2-methyl-1-propanol (1) of 91% enantiomeric purity in 82% yield via (i) Zr-catalyzed asymmetric methylalumination, (ii) iodination, and (iii) protection with TBSCl. After zincation of 1, its Pd-catalyzed cross-coupling with various organic halides can give various organic derivatives, including 3 and 4, which can serve as key intermediates for efficient and selective syntheses of deoxypolypropionates, such as doliculide and 2,4,6,8-tetramethyldecanoic acid, and other chiral compounds, such as callystatin A. Selective monocarboalumination of 1,4-pentadiene (5 equiv) gave, after oxidation, the expected product 5, but it was 0% ee. A plausible mechanism for racemization has been proposed and experimentally supported.Keywords
This publication has 28 references indexed in Scilit:
- All-Catalytic, Efficient, and Asymmetric Synthesis of α,ω-Diheterofunctional Reduced Polypropionates via “One-Pot” Zr-Catalyzed Asymmetric Carboalumination−Pd-Catalyzed Cross-Coupling Tandem ProcessJournal of the American Chemical Society, 2005
- An Efficient and General Method for the Synthesis of α,ω‐Difunctional Reduced Polypropionates by Zr‐Catalyzed Asymmetric Carboalumination: Synthesis of the Scyphostatin Side ChainAngewandte Chemie International Edition in English, 2004
- An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric C—C bond formationProceedings of the National Academy of Sciences, 2004
- Efficient and Selective Synthesis of Siphonarienolone and Related Reduced Polypropionates via Zr-Catalyzed Asymmetric CarboaluminationOrganic Letters, 2004
- Measurement of Barriers for Alkene Dissociation and for Inversion at Zirconium in a d0Zirconium−Alkyl−Alkene ComplexOrganometallics, 2000
- Zirconium-Catalyzed Enantioselective Alkylalumination of Monosubstituted Alkenes Proceeding via Noncyclic MechanismJournal of the American Chemical Society, 1996
- Zirconium-catalyzed enantioselective methylalumination of monosubstituted alkenesJournal of the American Chemical Society, 1995
- The role of torsional isomers of planarly chiral nonbridged bis(indenyl)metal type complexes in stereoselective propene polymerizationJournal of the American Chemical Society, 1993
- Lipase-catalyzed resolution of racemic 2-alkyl substituted 1-alkanolsTetrahedron: Asymmetry, 1993
- Acyclic stereocontrol in catalyzed intramolecular Diels-Alder cyclizations leading to octahydronaphthalenecarboxaldehydesJournal of the American Chemical Society, 1987