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Scientific article
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The Enantioselectivity and the Stereochemical Course of Copper-Catalyzed Intramolecular CH Insertions of Phenyliodonium Ylides

Published inHelvetica Chimica Acta, vol. 85, no. 2, p. 483-494
Publication date2002
Abstract

The Cu‐catalyzed intramolecular CH insertion of phenyliodonium ylide 1b was investigated at 0° in the presence of several chiral ligands. Enantioselectivities varied in the range 38–72%, and were higher than those resulting from reaction of the diazo compound 1c at 65°. The intramolecular insertion of the enantiomerically pure methyl diazoacetate (R)‐20 and of the corresponding phenyliodonium ylide (R)‐21 proceeded to (R)‐23 with retention of configuration with [Cu(hfa)₂] (hfa=hexafluoroacetylacetone=1,1,1,5,5,5‐hexafluoropentane‐2,4‐dione) and [Rh₂(OAc)₄]. These results are consistent with a carbenoid mechanism for the Cu‐catalyzed insertion with phenyliodonium ylides. However, the insertion of the perfluorosulfonated phenyliodonium ylide (R)‐29 afforded with [Cu(hfa)₂] as well as with [Rh₂(OAc)₄] the cyclopentanone derivative 30 as a cis/trans mixture with only 56–67% enantiomeric excess.

Citation (ISO format)
MULLER, Paul, BOLEA, Christelle. The Enantioselectivity and the Stereochemical Course of Copper-Catalyzed Intramolecular CH Insertions of Phenyliodonium Ylides. In: Helvetica Chimica Acta, 2002, vol. 85, n° 2, p. 483–494. doi: 10.1002/1522-2675(200202)85:2<483::AID-HLCA483>3.0.CO;2-Q
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ISSN of the journal0018-019X
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