Looking back: The asymmetric organocatalytic 1,4-addition of aldehydes to nitroolefins was studied by ESI-MS. Analysis of the back reaction starting from quasienantiomeric mass-labeled 1,4-adducts (see scheme) provided conclusive evidence for an enamine rather than an enol mechanism, and allowed identification of the enantioselectivity-determining step.
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Bächle et al. (2013) studied this question.
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