TY - JOUR
T1 - Origins of Protons in C-H Bond Insertion Products of Phenols
T2 - Proton-Self-Sufficient Function via Water Molecules
AU - Luo, Zhoujie
AU - Gao, Ya
AU - Zhu, Tong
AU - Zhang, John Zenghui
AU - Xia, Fei
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (Grants No. 21433004, 21403068, 21503132).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/8/31
Y1 - 2017/8/31
N2 - Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.
AB - Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.
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U2 - 10.1021/acs.jpca.7b06411
DO - 10.1021/acs.jpca.7b06411
M3 - Article
C2 - 28753009
AN - SCOPUS:85028668743
SN - 1089-5639
VL - 121
SP - 6523
EP - 6529
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 34
ER -