Running title
Chin. J. Chem.
Synergistic Palladium/Enamine Catalysis. Angew. Chem. Int. Ed. 2018,
Angew. Chem. 2017, 129, 7311-7314; c) Shi, Y.; Gao, Q.; Xu, S. Chiral
Bidentate Boryl Ligand Enabled Iridium-Catalyzed Enantioselective
C(sp3)-H Borylation of Cyclopropanes. J. Am. Chem. Soc. 2019, 141,
10599-10604; d) Zou, X.; Zhao, H.; Li, Y.; Gao, Q.; Ke, Z.; Xu, S. Chiral
Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp2)–
H Borylation of Diarylmethylamines. J. Am. Chem. Soc. 2019, 141,
5334 -5342; (e) Reyes, R. L.; Sato, M.; Iwai, T.; Sawamura, M.,
Asymmetric Synthesis of α-Aminoboronates via Rhodium-Catalyzed
Enantioselective C(sp3)–H Borylation. J. Am. Chem. Soc. 2020, 142,
589-597. (f) Reyes, R. L.; Iwai, T.; Maeda, S.; Sawamura, M. Iridium-
Catalyzed Asymmetric Borylation of Unactivated Methylene C(sp3)–H
Bonds. J. Am. Chem. Soc. 2019, 141, 6817–6821 (g) G. R. Genov, J. L.
Douthwaite, A. S. K. Lahdenperä, D. C. Gibson, R. J. Phipps, Science
2020, 367, 1246-1251; (h) Zhan, M.; Song, P.; Jiao, J.; Li, P. Novel Chiral
Ligands-Enabled Transition-Metal-Catalyzed Asymmetric C-H
Borylation. Chin. J. Chem. 2020, 38, 665-667.
57, 2707-2711; (c) Aitken, D. J.; Caboni, P.; Eijsberg, H.; Frongia, A.;
Guillot, R.; Ollivier, J.; Piras, P. P.; Secci, F. Catalytic Enantioselective
Synthesis of α-Arylaminocyclobutanones. Adv. Synth. Catal. 2014, 356,
941-945; d) Mailhol, D.; Duque, M. d. M. S.; Raimondi, W.; Bonne, D.;
Constantieux, T.; Coquerel, Y.; Rodriguez, J. Enantioselective
Organocatalytic Michael Addition of Cyclobutanones to Nitroalkenes.
Adv. Synth. Catal. 2012, 354, 3523-3532.
(a) Zhong, C.; Huang, Y.; Zhang, H.; Zhou, Q.; Liu, Y.; Lu, P.
Enantioselective Synthesis of 3-Substituted Cyclobutenes via Catalytic
Conjugate Addition/Trapping Strategies. Angew. Chem. Int. Ed. 2020,
59, 2750-2754; (b) Y.-J. Chen, T.-J. Hu, C.-G. Feng, G.-Q. Lin, Chem.
Commun. 2015, 51, 8773-8776; (c) Xia, J.; Nie, Y.; Yang, G.; Liu, Y.;
Gridnev, I. D.; Zhang, W. Ir-Catalyzed Asymmetric Hydrogenation of α-
Alkylidene β-Lactams and Cyclobutanones. Chin. J. Chem. 2018, 36,
612-618
Misale, A.; Niyomchon, S.; Luparia, M.; Maulide, N. Asymmetric
Palladium-Catalyzed Allylic Alkylation Using Dialkylzinc Reagents: A
Remarkable Ligand Effect. Angew. Chem. Int. Ed. 2014, 53, 7068-
7073.
(a) Wu, Q.-F.; Wang, X.-B.; Shen, P.-X.; Yu, J.-Q. Enantioselective C–H
Arylation and Vinylation of Cyclobutyl Carboxylic Amides. ACS Catal.
2018, 8, 2577-2581; b) Xiao, K.-J.; Lin, D. W.; Miura, M.; Zhu, R.-Y.;
Gong, W.; Wasa, M.; Yu, J.-Q. Palladium(II)-Catalyzed Enantioselective
C(sp3)–H Activation Using a Chiral Hydroxamic Acid Ligand. J. Am.
Chem. Soc. 2014, 136, 8138-8142.
Wang, M.; Lu, P., Catalytic approaches to assemble cyclobutane motifs
in natural product synthesis. Org. Chem. Front. 2018, 5, 254-259.
Leonori, D.; Aggarwal, V. K., Reagent-Controlled Lithiation–Borylation.
In Synthesis and Application of Organoboron Compounds, Fernández,
E.; Whiting, A., Eds. Springer International Publishing: Cham, 2015; pp
271-295.
Man, H.-W.; Hiscox, W. C.; Matteson, D. S. A Highly Enantioselective
and Diastereoselective Synthesis of Cyclobutanes via Boronic Esters.
Org. Lett. 1999, 1, 379-382.
Coote, S. C.; Bach, T. Enantioselective Intermolecular [2+2]
Photocycloadditions of Isoquinolone Mediated by a Chiral Hydrogen-
Bonding TemplateJ. Am. Chem. Soc. 2013, 135, 14948-14951.
Guisán-Ceinos, M.; Parra, A.; Martín-Heras, V.; Tortosa, M.
Enantioselective Synthesis of Cyclobutylboronates via a Copper-
Catalyzed Desymmetrization Approach. Angew. Chem. Int. Ed. 2016,
55, 6969-6972.
Clement, H. A.; Boghi, M.; McDonald, R. M.; Bernier, L.; Coe, J. W.;
Farrell, W.; Helal, C. J.; Reese, M. R.; Sach, N. W.; Lee, J. C.; Hall, D. G.
High-Throughput Ligand Screening Enables the Enantioselective
Conjugate Borylation of Cyclobutenones to Access Synthetically
Versatile Tertiary Cyclobutylboronates. Angew. Chem. Int. Ed. 2019,
58, 18405-18409.
He, J.; Shao, Q.; Wu, Q.; Yu, J.-Q. Pd(II)-Catalyzed Enantioselective
C(sp3 )–H Borylation. J. Am. Chem. Soc. 2017, 139, 3344-3347.
(a) Reyes, R. L.; Harada, T.; Taniguchi, T.; Monde, K.; Iwai, T.;
Sawamura, M. Enantioselective Rh- or Ir-catalyzed Directed C(sp3)–H
Borylation with Phosphoramidite Chiral Ligands. Chem. Lett. 2017, 46,
1747-1750; (b) Su, B.; Zhou, T.-G.; Xu, P.-L.; Shi, Z.-J.; Hartwig, J. F.
Enantioselective Borylation of Aromatic C−H Bonds with Chiral
Dinitrogen Ligands. Angew. Chem. Int. Ed. 2017, 56, 7205-7208;
(a) Murakami, R.; Tsunoda, K.; Iwai, T.; Sawamura, M. Stereoselective
C-H Borylations of Cyclopropanes and Cyclobutanes with Silica ‐
Supported Monophosphane–Ir Catalysts. Chem. - Eur. J. 2014, 20,
13127-13131. (b) Giri, R.; Yu, J.-Q. Palladium-catalyzed asymmetric
iodination of unactivated C-H bonds under mild conditions. Angew.
Chem. Int. Ed. 2005, 44, 2112-2115; (c) Saint-Denis, T. G.; Zhu, R.-Y.;
Chen, G.; Wu, Q.-F.; Yu, J.-Q. Enantioselective C(sp3)-H bond
activation by chiral transition metal catalysts. Science 2018, 359, 759
-770. (d) Zhang, Q.; Shi, B.-F. From Reactivity and Regioselectivity to
Stereoselectivity: An Odyssey of Designing PIP Amine and Related
Directing Groups for C—H Activation. Chin. J. Chem. 2019, 37, 647-
656; (e) Zhou, T.; Jiang, M.-X.; Yang, X.; Yue, Q.; Han, Y.-Q.; Ding, Y.;
Shi, B.-F. Synthesis of Chiral β -Lactams by Pd-Catalyzed
Enantioselective Amidation of Methylene C(sp3)-H Bonds. Chin. J.
Chem. 2020, 38, 242-246.
Bonet, A.; Odachowski, M.; Leonori, D.; Essafi, S.; Aggarwal, V. K.,
Enantiospecific sp2-sp3 coupling of secondary and tertiary boronic
esters. Nat. Chem. 2014, 6, 584-589.
Armstrong, R. J.; Niwetmarin, W.; Aggarwal, V. K. Synthesis of
Functionalized Alkenes by a Transition-Metal-Free Zweifel Coupling.
Org. Lett. 2017, 19, 2762-2765.
Sandford, C.; Aggarwal; V. K. Stereospecific functionalizations and
transformations of secondary and tertiary boronic esters. Chem.
Commun. 2017, 53, 5481-5494.
Nguyen, D.-V.; Gravel, E.; Buisson, D.-A.; Nicolas, M.; Doris, E.;
Enantioselective synthesis of a cyclobutane analogue of Milnacipran.
Org. Chem. Front. 2017, 4, 1276-1280.
(a) Boller, T. M.; Murphy, J. M.; Hapke, M.; Ishiyama, T.; Miyaura, N.;
Hartwig, J. F., Mechanism of the Mild Functionalization of Arenes by
Diboron Reagents Catalyzed by Iridium Complexes. Intermediacy and
Chemistry of Bipyridine-Ligated Iridium Trisboryl Complexes. J. Am.
Chem. Soc. 2005, 127, 14263-14278; (b) Huang, G.; Kalek, M.; Liao,
R.-Z.; Himo, F., Mechanism, reactivity, and selectivity of the iridium-
catalyzed C(sp3)-H borylation of chlorosilanes. Chem. Sci. 2015, 6,
1735-1746.
(a) Ghaffari, B.; Preshlock, S. M.; Plattner, D. L.; Staples, R. J.; Maligres,
P. E.; Krska, S. W.; Maleczka, R. E.; Smith, M. R. Silyl Phosphorus and
Nitrogen Donor Chelates for Homogeneous Ortho Borylation Catalysis.
J. Am. Chem. Soc. 2014, 136, 14345-14348; (b) Wang, G.; Liu, L.;
Wang, H.; Ding, Y.-S.; Zhou, J.; Mao, S.; Li, P. N,B-Bidentate Boryl
Chin. J. Chem. 2019, 37, XXX-XXX
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
This article is protected by copyright. All rights reserved.