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Catalysis Science & Technology
Page 4 of 6
COMMUNICATION
Journal Name
Based on the reported works,12,18 the previous studies,15 and the
control experiments (S4), a plausible reaction pathway of the C-N
bond cleavage process was proposed (Scheme 1). Combing the
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Piers’ silane activation mode18 with
Itohs' four-membered
transition state,19 the hydroborate metal base facilitates the
hydride transfer from Si to B, producing a possible active specie
borane/silane complex A, which intermediate transfers the hydride,
the silyl residue to the electrophilic carbon and the oxygen,
respectively. Then, an another borane/silane intermediate
transfers a hydride to the carbon of B and the silyl residue to the
nitrogen function.12 After that, the C-N bond is cleaved to produce
silyl ether and silyl amine, which could smoothly afford the final
products under acidic conditions. An alternative, but less likely
pathway (see S4.4), invoves the formation of the borate species
NaBEt3R*, which could provide a possible borane/silane complex
that acts as the active species for the C-N bonds cleavage.
3
4
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In summary, we have developed the first approach for the
selective cleavage of inert C-N bonds in tertiary amides with
triethoxysilane under mild conditions, using a really simple hydride
catalyst in the absence of additives. Featuring highly efficient and
excellent selectivity, this novel method is practical and general
process for the reductive cleavage of unactivated tertary amides,
which is useful for a variety of value-added applications.
7
We gratefully acknowledge the financial support from China
Postdoctoral Science Foundation (2017M621972), Zhejiang Post-
Doctoral Preferential Fund Project (zj20180084), Natural Science
Foundation of Zhejiang Province (LQ19B020001), Chemical
Engineering & Technology of Zhejiang Province First-Class Discipline
(Taizhou University), Science and Technology Plan Project of
Taizhou (1803gy04), Project of Taizhou University Fund for Excellent
Young Scholars, and Zhejiang University Student Science and
Technology Innovation Activity Plan Project. The authors also thank
Lanzhou University for the support.
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Conflicts of interest
There are no conflicts to declare.
Notes and references
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