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ChemComm
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COMMUNICATION
Journal Name
In our previous work, we have suggested that (HMe2SiCH2)2
might facilitate an intramolecular Si/ketone activation manner that
makes (HMe2SiCH2)2 superior to one silicon-centered hydrosilanes
for reduction/lactonization of keto acids.12 To examine whether a
similar activation manner as shown by TS-3 is involved in the
deoxygenation of alcohols, we performed the control experiments
using 4a and 4b (Scheme 3). Despite the silyl ether moieties in 4a
and 4b are sterically similar to each other, only 4b is potentially
capable of an intramolecular Si/O activation. As expected, removal
of the phenyl ether was observed as the predominant path in the
reaction of 4a, while that of 4b gave the desired 3a in 74% yield. In
addition, the reaction of 4b with EtMe2SiH indeed gave 3a, but only
in 18% yield. The contrasting results from these two reactions using
4b suggested that in addition to the proposed intramolecular Si/O
activation, (HMe2SiCH2)2 should play other important roles for
promoting the deoxygenation approach. More detailed studies are
currently underway.
In conclusion, (HMe2SiCH2)2 has been used as a useful reagent
for B(C6F5)3-catalyzed chemoselective deoxygenation of ether-
substituted alcohols and carbonyl compounds. The approach shows
good tolerance of ether, aryl halide and alkene, giving the
corresponding alkane in good yields. (HMe2SiCH2)2 has been
proposed to facilitate an intramolecular Si/O activation, making this
reagent superior to traditional one silicon-centered hydrosilanes.
More detailed studies and applications of this approach are
currently underway.
DOI: 10.1039/C8CC01163J
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4 | J. Name., 2012, 00, 1-3
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