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Mechanistic Studies on Pd(MPAA)-Catalyzed Enantioselective C–H Activation Reactions

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Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods

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Abstract

A combined ion-mobility mass spectrometry (IM-MS) and DFT study has been carried out to investigate Pd/MPAA(mono-N-protected amino acid)-catalyzed direct asymmetric C–H activation reactions of several prochiral substrates. The IM-MS experiments reveal that the activation of C–H bond can be achieved in PdII(MPAA)(substrate) complex which supports that the N-protecting group acts as proton acceptor. DFT studies lead to the establishment of a chirality relay model which successfully explains the enantioselectivity for all the relevant reactions studied. The enantioselectivity originates from the rigidity of the bidentate MPAA and rigid coordination of the substrate. The effect of bulkiness of the N-protecting group on enantioselectivity is also discussed.

The results presented in this chapter have been published in the following article:

Cheng, G.-J.; P.; Chen, P.; Sun, T.-Y.; Zhang, X.; Yu, J.-Q.; Wu, Y.-D. Chem. Eur. J. 2015, 21, 11180.

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  1. Laboratory of Computational Chemistry and Drug Design and Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen, China

    Gui-Juan Cheng

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Correspondence to Gui-Juan Cheng .

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Cheng, GJ. (2017). Mechanistic Studies on Pd(MPAA)-Catalyzed Enantioselective C–H Activation Reactions. In: Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-4521-9_4

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