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Dalton Transactions
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ARTICLE
Journal Name
Med. Chem., 2011, 54, 3451–3479.
There is also a third possibility of R–C(H)(OBpin)(NR′R′′) (C-C) σ-
bond metathesis, which is found under high HBpin
concentrations (Scheme S1c). Presumably under the large
HBpin concentration, amide nitrogen center is coordinated with
excess HBpin producing [C1], which undergoes the cleavage of
the C–C bond by its reaction with complex [B] producing the
product [P2] and [D2] as an intermediate. Complex [D2] reacts
with HBpin to regenerate the active species [B].
3
4
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5
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A. M. Smith and R. Whyman, Chem. Rev., 2014, 114, 5477–
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H
Bpin
[Th]
k2
R'
H
[B]
O
R
HBpin
N
k3
R''
[S]
k-2
Me-Bpin
[Th1]
HBpin
[Th]
7
8
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R'
H
R
H
[A]
R''
N
k1
+ HBpin
[Th]
O
k5
[C]
BpinOBpin
k4
(rds)
Bpin
[Th]
O
HBpin
[D]
R
H
R
N
R'' = Aryl/alkyl (tertiary amides)
Bpin (secondary amides)
R''
H
[P]
Scheme 1. Proposed Mechanism of Hydroboration of amides.
Conclusions
The selective hydroboration of amides (tertiary/secondary/primary)
with HBpin to the corresponding deoxygenated amine/amine-
borane adducts promoted by the Cp*2ThMe2 complex (Th1) has been
established. The succesful gram-scale reaction makes this catalytic
system usufull for synthetic purposes. The development of highly
active actinide catalysts based on these new findings are currently
underway in our laboratory.
9
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Acknowledgements
This work was supported by the Israel Science Foundation
administered by the Israel Academy of Science and Humanities
under Contract No. 184/18. by the PAZY Foundation Fund (ID
128-2020) administered by the Israel Atomic Energy
Commission. S. S. thanks the ‘Nancy and Stephen Grand
Technion Energy Fellowship’.
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