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Journal of the American Chemical Society
AUTHOR INFORMATION
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Corresponding Author
sylviane.sabo@lccꢀtoulouse.fr, sebastien.bontemps@lccꢀ
toulouse.fr
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Author Contributions
All authors have given approval to the final version of the manuꢀ
script.
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ACKNOWLEDGMENT
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CSC is gratefully acknowledged for the PhD fellowship of G.J..
Support from CNRS and the ANR (Programme blanc
“IRONHYC” ANRꢀ12) is also acknowledged. We thank Dr.
Christian Bijani for NMR analyses.
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Scheme 3: Reactions of inꢀsitu generated 2 affording compounds
5ꢀ10.
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We used both 13CO2 and 12CO2 to confirm by NMR and
HRMS that the methylene carbon atom within 3-10 resulted
from the reduction of CO2. NMR data for the bis(boryl)acetal
2 and for the resulting compounds 3ꢀ10 are provided in Table
2.
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1
S4. The important variations of 13C and H NMR chemical
shifts (from δ(13C) = 32.6 and δ(1H) = 3.88 for compound 9 to
δ(13C) = 156.5 and δ(1H) = 7.73 for compound 4), indicating
different types of methylene, highlight the versatile reactivity
of compound 2. The experiments performed in NMR tubes
allowed detailed and convenient monitoring. In a next stage,
we sought for isolation of the functionalized products and
compounds 8 and 9 were selected. On a 10ꢀfold scale up synꢀ
thesis, compound 2 was selectively generated at 60 °C in 10
min, and subsequently trapped to afford compounds 8 and 9 in
98 and 37 % isolated yields based on the trapping agent, reꢀ
spectively. A 100ꢀfold scale up synthesis led to compound 8 in
2 days at room temperature with a 70 % (106.2 mg) isolated
yield based on 9ꢀBBN.
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To conclude, we report herein the use of a (dihydrido)iron
complex in the reduction of CO2 into either bis(boryl)acetal or
methoxyborane depending on the hydroborane used as reductꢀ
ant. Selective reduction of CO2 to the acetal level and subseꢀ
quent functionalization in a oneꢀpot twoꢀsteps procedure,
allowed to transform CO2 into methylene and to considerably
enlarge the scope of accessible functions by generating new Cꢀ
N but also CꢀO and CꢀC bonds. Our results further highlight
the importance of metal hydride complexes in the controlled
transformation of CO2. We are currently conducting mechanisꢀ
tic investigation to understand and improve the catalytic sysꢀ
tem and pursuing research on the specific reactivity of
bis(boryl) and / or bis(silyl)acetal compounds.23
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ASSOCIATED CONTENT
Experimental details and NMR data. “This material is available
free of charge via the Internet at http://pubs.acs.org.”
12.
characterization of
reduction of CO2: see Courtemanche, M.ꢀA.; Pulis, A. P.; Rochette, E.;
Very recently, Fontaine, Stephan et al. reported the first XꢀRay
a
bis(boryl)acetal compound resulting from the
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