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Journal of the American Chemical Society
O
(1) Talele, T. T. The "Cyclopropyl Fragment" is a Versatile Player
that Frequently Appears in Preclinical/Clinical Drug Molecules. J.
Med. Chem. 2016, 59, 8712-8756.
(2) Taylor, R. D.; MacCoss, M.; Lawson, A. D. Rings in drugs. J.
Med. Chem. 2014, 57, 5845-59.
(3) Rubin, M.; Rubina, M.; Gevorgyan, V. Transition Metal
Chemistry of Cyclopropenes and Cyclopropanes. Chem. Rev. 2007,
IM8
Bpin
CuCl + L
NaOEt
NaCl
1
2
3
4
5
6
7
8
9
Bpin
I
Cu (L)
Bpin
Bpin
I
Bpin
R
OCu (L)
R
O
L
Cu OEt
IM2
Bpin
B2pin2
Bpin
IM8
Bpin
R
IM3
EtOBpin
1
07, 3117-3179.
B2pin2
(
4) Ebner, C.; Carreira, E. M. Cyclopropanation Strategies in Recent
I
Cu (L)
OBpin
Bpin
Total Syntheses. Chem. Rev. 2017, 117, 11651-11679.
O
L
Cu Bpin
(5) Sayes, M.; Benoit, G.; Charette, A. B. Borocyclopropanation of
Styrenes Mediated by UV-light Under Continuous Flow Conditions.
Angew. Chem. Int. Ed. 2018, 57, 13514-13518.
L
Cu
Bpin
IM4
IM1
R
Bpin
IM7
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(6)
Benoit,
G.;
Charette,
A.
B.
Diastereoselective
pinBOBpin
OBpin
H
Borocyclopropanation of Allylic Ethers Using a Boromethylzinc
Carbenoid. J. Am. Chem. Soc. 2017, 139, 1364-1367.
CO
2
B pin
2
Bpin
R
L
Cu OBpin
I
Cu (L)
(7) Murai, M.; Mizuta, C.; Taniguchi, R.; Takai, K. Synthesis of
IM6
Bpin IM5
Borylcyclopropanes by Chromium-Promoted Cyclopropanation of
Unactivated Alkenes. Org. Lett. 2017, 19, 6104-6107.
Bpin
(8) Carreras, J.; Caballero, A.; Perez, P. J. Enantio- and
R
Bpin
Diastereoselective Cyclopropanation of 1-Alkenylboronates:
Synthesis of 1-Boryl-2,3-Disubstituted Cyclopropanes. Angew. Chem.
Int. Ed. 2018, 57, 2334-2338.
Fig. 6. Plausible reaction mechanism.
(9) Amenos, L.; Trulli, L.; Novoa, L.; Parra, A.; Tortosa, M.
In summary, a novel copper-catalyzed stereodefined
procedure for the selective synthesis of cyclopropyl
bis(boronates) from terminal alkenes has been developed.
Various aliphatic alkenes were transformed into the desired
bis(boronate ester)-substituted cyclopropanes in moderate to
good yields. Synthetic transformations of the cyclopropyl
bis(boronate) products clearly demonstrate the utility of this
process. Finally, a possible reaction pathway is proposed, and
a detailed computational study of the mechanism is in
progress.
Stereospecific Synthesis of alpha-Hydroxy-Cyclopropylboronates
from Allylic Epoxides. Angew. Chem. Int. Ed. 2019, 58, 3188-3192.
(10) Zhong, C.; Kunii, S.; Kosaka, Y.; Sawamura, M.; Ito, H.
Enantioselective Synthesis of trans-Aryl- and -Heteroaryl-Substituted
Cyclopropylboronates by Copper(I)-Catalyzed Reactions of Allylic
Phosphates with a Diboron Derivative. J. Am. Chem. Soc. 2010, 132,
1
1440–11442.
(11) Ito, H.; Kosaka, Y.; Nonoyama, K.; Sasaki, Y.; Sawamura, M.
Synthesis of Optically Active Boron-Silicon Bifunctional
Cyclopropane Derivatives Through Enantioselective Copper(I)-
Catalyzed Reaction of Allylic Carbonates with a Diboron Derivative.
Angew. Chem. Int. Ed. 2008, 47, 7424-7427.
(12) Shintani, R.; Fujie, R.; Takeda, M.; Nozaki, K. Silylative
Cyclopropanation of Allyl Phosphates with Silylboronates. Angew.
Chem. Int. Ed. 2014, 53, 6546-9549.
ASSOCIATED CONTENT
Supporting Information.
(13) Parra, A.; Amenos, L.; Guisan-Ceinos, M.; Lopez, A.; Garcia
Optimization details, general procedures, analytic data, and NMR
Ruano, J. L.; Tortosa, M. Copper-Catalyzed Diastereo- and
Enantioselective Desymmetrization of Cyclopropenes: Synthesis of
Cyclopropylboronates. J. Am. Chem. Soc. 2014, 136, 15833-15836.
(14) He, J.; Jiang, H.; Takise, R.; Zhu, R. Y.; Chen, G.; Dai, H. X.;
Dhar, T. G.; Shi, J.; Zhang, H.; Cheng, P. T.; Yu, J. Q. Ligand-
Promoted Borylation of C(sp(3))-H Bonds with Palladium(II)
Catalysts. Angew. Chem. Int. Ed. 2016, 55, 785-789.
spectra.
AUTHOR INFORMATION
Corresponding Author
(15) (a) Peng, J.-B.; Wu, F.-P.; Wu, X.-F. First-Row Transition-
Metal-Catalyzed Carbonylative Transformations of Carbon
Electrophiles. Chem. Rev. 2019, 119, 2090-2127. (b) Peng, J.-B.;
Geng, H.-Q.; Wu, X.-F. The Chemistry of CO: Carbonylation. Chem
*
E-mail: xiao-feng.wu@catalysis.de
*E-mail: todd.marder@uni-wuerzburg.de
2
019, 5, 526-552.
(16) (a) Batsanov, A. S.; Cabeza, J. A.; Crestani, M. G.; Fructos, M.
Notes
R.; García-Álvarez, P.; Gille, M.; Lin, Z.; Marder, T. B. Fully
Borylated Methane and Ethane by Ruthenium-Mediated Cleavage and
Coupling of CO. Angew. Chem. Int. Ed. 2016, 55, 4707-4710. (b)
Goudreau, S. R.; Charette, A. B. Defying Ring Strain: New
Approaches to Cyclopropanes. Angew. Chem. Int. Ed. 2010, 49, 486-
There is no conflict of interests to declare.
ACKNOWLEDGMENT
4
88.
F.-P.W. and X.L. thank the Chinese Scholarship Council for a
PhD Scholarship and a Sabbatical Leave Postdoctoral Fellowship,
respectively. We thank the analytical department of the Leibniz-
Institute for Catalysis at the University of Rostock for their
assistance. We also thank Dr. Anke Spannenberg (LIKAT) for the
X-ray crystal structure analysis of compounds 2 and 18. U.R. and
T.B.M. thank the Julius-Maximilians-Universität Würzburg for
support.
(17) (a) Wu, F.-P.; Yuan, Y.; Schünemann, C.; Kamer, P. C. J.; Wu,
X.-F. Copper-Catalyzed Regioselective Borocarbonylative Coupling
of Unactivated Alkenes with Alkyl Halides: Synthesis of β -Boryl
Ketones. Angew. Chem. Int. Ed. 2020, 59, 10451-10455. (b) Yuan,
Y.; Wu, F.-P.; Xu, J.-X.; Wu, X.-F. Four-Component
Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd
Catalysis: Access to β -Boryl Ketones and β -Boryl Vinyl Esters.
Angew. Chem. Int. Ed. 2020, 59, doi: anie.202006427.
(18) Yu, X.; Zhao, H.; Xi, S.; Chen, Z.; Wang, X.; Wang, L.; Lin, L.
Q. H.; Loh, K. P.; Koh, M. J. Site-selective alkene borylation enabled
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