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While the reactions were typically carried out in one pot, the γ-aminoxy-α,β-unsaturated ester intermediates could be isolated and characterized. See Supporting Information for full characterization of the γ-aminoxy-α,β-unsaturated ester intermediate (7) of Table 2, entry 14
-
While the reactions were typically carried out in one pot, the γ-aminoxy-α,β-unsaturated ester intermediates could be isolated and characterized. See Supporting Information for full characterization of the γ-aminoxy-α,β-unsaturated ester intermediate (7) of Table 2, entry 14.
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One of the reviewers raised an interesting possibility that the reaction proceeds by an initial N -nitroso aldol reaction followed by a [2,3]-sigmatropic rearrangement of the resulting α- N -phenylhydroxyamino-β,γ- unsaturated ester to give the γ-aminoxy-α,β-unsaturated ester intermediate. While we cannot rule out this possibility, related studies of nitroso aldol reactions with aldehydes and ketones suggest that O - instead of N -nitroso aldol products are likely to be preferred under the current reaction conditions as a result of the difference in basicities of the oxygen and nitrogen atoms. See ref 2a and
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One of the reviewers raised an interesting possibility that the reaction proceeds by an initial N -nitroso aldol reaction followed by a [2,3]-sigmatropic rearrangement of the resulting α- N -phenylhydroxyamino-β,γ- unsaturated ester to give the γ-aminoxy-α,β-unsaturated ester intermediate. While we cannot rule out this possibility, related studies of nitroso aldol reactions with aldehydes and ketones suggest that O-instead of N -nitroso aldol products are likely to be preferred under the current reaction conditions as a result of the difference in basicities of the oxygen and nitrogen atoms. See ref 2a and
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