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We predicted that uncatalyzed Mukaiyama aldol reactions are under the control of the geminal bond participation. At the transition state of the model reaction, addition of CH 2 O and CH 2 CH(OSiH 3 ), the interbond energy IBE is negative between the σ-bonding orbital at the Z-position of the enolate terminal and πCO∗, and positive between that at the E-position and πCO∗. These...
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