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The regio- and diastereoselective oxidative cyclization of alkenes using an achiral λ3-iodane has recently attracted much attention, see
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N2 must give the R isomer. For the acetoxylactonization, a 1, 3-dioxolan-2-yl cation may serve as an intermediate in the double inversion. Results for the enantioselectivity of the minor γ lactone product are rationalized by a combination of these reaction pathways.
-
The absolute stereochemistry of the γ-lactone products 9 a and 11 a depended on the reaction conditions. There are some conceivable reaction pathways for the formation of the minor γ lactone: 1) The internal carboxylic acid participates toward the benzylic position of the intermediate A. In this case, the (S)- isomer of the γ lactone must form in the reactions with 1-6, judging from the preferential formation of the (S)-isomer of the δlactone. 2) Dioxytosylation of the vinyl group, followed by internal nucleophilic substitution at the benzylic position. The SN1 route must give a racemic product, and the SN2 must give the R isomer. For the acetoxylactonization, a 1, 3-dioxolan-2-yl cation may serve as an intermediate in the double inversion. Results for the enantioselectivity of the minor γ lactone product are rationalized by a combination of these reaction pathways.
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Experimental evidence for secondary I-O interactions in solution was obtained in a complex of PhI+OH and 18-crown-6 by cold-spray ionization mass spectroscopy.[19b] Intramolecular interaction has been discussed in the solid state.[4b, c, 10d, e]
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n (n = 0-2). Thus, the oxygen atom bound at the ortho position of the aryliodane has little interfering effect on the solvent coordination to the iodonium ion.
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Electrospray ionization mass spectrometry of 1-(diacetoxyiodo)- 2-methoxy benzene showed a similar result to that of 1-(diac- etoxyiodo)-2, 4, 6-trimethylbenzene in the relative intensities of M+-(MeCN)n (n = 0-2). Thus, the oxygen atom bound at the ortho position of the aryliodane has little interfering effect on the solvent coordination to the iodonium ion.
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