10.1002/anie.201801814
Angewandte Chemie International Edition
COMMUNICATION
Scheme 3. Hypothetical mechanism.
carbonylative coupling reactions for primary and secondary alkyl
iodides (see SI, page S19).[12b]
In conclusion, we have developed
hydroxymethylation reaction of alkyl iodides to construct one
carbon-extended alcohols under mild conditions. This protocol is
a Cu-catalyzed
H
H
O[Si]
R
E
compatible with
a broad range of functional groups and
MeIPrCuH
heterocycles. Mechanistic experiments are consistent with a
metal-free radical atom transfer carbonylation of the alkyl iodide
followed in tandem by a CuH-mediated reduction sequence.
LiOMe
O
[Si]-H
MeIPrCuI
LiI
H
R
R
H
H
R
C
OCuMeIPr
MeIPrCuOMe
D
O
Acknowledgements
MeIPrCuH
[Si]I
[Si]·
RI
I
I
[Si]-H
B
R
Funding was provided by the NSF (CHE-1664632).
[Si]-OMe
R
Keywords: carbonylation • copper • alcohols • hydroformylation
O
CO
• hydrides
R
A
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under conditions specified in Table 1, entry 2. This low level of
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assistance of a strong nucleophile to shift the equilibrium, it is difficult to
furnish iodide transfer.
[6]
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Selected examples of cross-coupling with organometallic hydroxymethyl
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