ISSN:
0947-6539
Keywords:
alkynes
;
asymmetric syntheses
;
cyclopropanes
;
spiro compounds
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A variety of chiral, nonracemic 2-alkoxy-1-alkynylcyclopropanes 7 were synthesized in good to very good yields from enantiomerically pure glycidol derivatives (glycidol tosylate, epichlorohydrin) by boron trifluoride promoted addition of lithium trimethylsilylacetylide followed by protection of the secondary hydroxyl group and finally a diastereoselective γ-elimination. The 2-ethoxy derivative (S,R)-7 b was deprotonated with n-butyllithium, and the resulting 1-lithio-2-ethoxy derivative (S,R)-20 functionalized by treatment with oxygen followed by tosyl chloride. Protodesilylation and catalytic hydrogenation smoothly furnished 1-ethenylcyclopropyl sulfonates, which underwent a clean Pd0-catalyzed SN2′-type substitution with dimethyl propargylsodiummalonate to give the (E)-configurated enyne (R,E)-26 with a methylenecyclopropane end group. A diastereoselective Pauson-Khand reaction completed the sequence to give the enantiomerically pure spirocyclopropaneannelated bicyclo[3.3.0]octane derivative 31.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19960020514
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