ISSN:
0947-6539
Keywords:
alkenes
;
asymmetric synthesis
;
natural products
;
Lewis acids
;
phosphane oxides
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A general, highly efficient methodology for obtaining both syn and anti β-hydroxyphosphine oxides by reduction of the corresponding β-ketophosphine oxides is described. The nature of the Lewis acid was found to be pivotal in determining the outcome of these reactions. Strongly chelating TiCl4 led to the anti isomer in high diastereoisomeric excess in noncoordinating solvents (CH2Cl2) at -78°C with BH3/py as reducing agent, while nonchelating CeCl3 gave a high excess of the syn isomer in coordinating solvents (THF) at the same temperature with LiBH4 as reducing agent. In the latter case, CeCl3 is essential in achieving high yields and stereoselectivity, since it allows the reaction to be performed at low temperatures. Otherwise, higher temperatures (0°C) are required, which lower both yields and selectivities. Moreover, each step of the protocol for the synthesis of stereodefined disubstituted olefins from alkylphosphine oxides (Warren's modification of the Horner procedure) has been optimized, and the optimized procedure has been applied to the synthesis of muscalure, the pheromone of the domestic fly.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970031209
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