Journal of the American Chemical Society
Page 8 of 10
Rahim, A.; Feng, J.; Gu, Z. 1,4-Migration of Transition
Metals in Organic Synthesis. Chin. J. Chem. 2019, 37, 929–
945.
(9) (a) Dyker, G. Palladium-Catalyzed C-H Activation of
Methoxy Groups: A Facile Synthesis of Substituted 6H-
Dibenzo[b,d]pyrans. Angew. Chem. Int. Ed. 1992, 31, 1023–
1025. (b) Dyker, G. Palladium-Catalyzed C–H Activation of
1
2
3
4
5
6
7
8
ACKNOWLEDGMENT
This work was financially supported by Oril Industrie,
affiliated to Les Laboratoires Servier, and the University of
Basel. We thank Dr. Lucile Vaysse-Ludot, Dr. R. Tamion
and J. Fournier, ORIL Industrie, for fruitful discussions and
constant support, Dr. D. Häussinger, University of Basel,
for NMR experiments, and Dr. M. Pfeffer, University of
Basel, for MS analyses.
tert-Butyl Groups:
A
Simple Synthesis of 1,2-
Dihydrocyclobutabenzene Derivatives. Angew. Chem. Int. Ed.
1994, 33, 103–105. (c) Dyker, G. Palladium-Catalyzed C–H
Activation at Methoxy Groups: Regiochemistry of the
Domino Coupling Process. Chem. Ber. 1994, 127, 739–742.
(10) (a) Baudoin, O.; Herrbach, A.; Guéritte, F. The
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Palladium‐Catalyzed
C–H
Activation
of
Benzylic
REFERENCES
gem‐Dialkyl Groups. Angew. Chem. Int. Ed. 2003, 42, 5736-
5740. (b) Hitce, J.; Retailleau, P.; Baudoin, O. Palladium-
Catalyzed Intramolecular C(sp3)–H Functionalization:
Catalyst Development and Synthetic Applications. Chem.
Eur. J. 2007, 13, 792–799. (c) Motti, E.; Catellani, M.
Catalytic Dehydrogenation of o-Alkylated or o-Alkoxylated
Iodoarenes with Concomitant Hydrogenolysis. Adv. Synth.
Catal. 2008, 350, 565–569. (d) Bheeter, C. B.; Jin, R. ; Bera,
J. K.; Dixneuf, P. H. ; Doucet, H. Palladium-Catalysed
Dehydrogenative sp3 C–H Bonds Functionalisation into
Alkenes: A Direct Access to N-Alkenylbenzenesulfonamides.
Adv. Synth. Catal. 2014, 356, 119–124.
(1) Faust, R. Fascinating Natural and Artificial Cyclopropane
Architectures. Angew. Chem. Int. Ed. 2001, 40, 2251–2253.
(2) (a) 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. (b) Časar, Z.
Synthetic Approaches to Contemporary Drugs that Contain
the Cyclopropyl Moiety. Synthesis 2020, 52, 1315–1345.
(3) (a) Roy, M.-N.; Lindsay, V. N. G.; Charette, A. B.
Cyclopropanation Reactions. In Science of Synthesis, De
Vries, J. G.; Molander, G. A.; Evans, P. A., Eds.; Thieme:
Stuttgart, 2011; Vol. 1, pp 731–817. (b) Kulinkovich, O. G.
Cyclopropanes in Organic Synthesis, John Wiley & Sons,
Inc.: Hoboken, 2015.
(4) (a) Chen, D. Y.-K.; Pouwerb, R. H.; Richard, J.-A. Recent
Advances in the Total Synthesis of Cyclopropane-Containing
Natural Products. Chem. Soc. Rev. 2012, 41, 4631–4642. (b)
Ebner, C.; Carreira, E. M. Cyclopropanation Strategies in
Recent Total Syntheses. Chem. Rev. 2017, 117,
11651−11679.
(11) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S.
L. Catalysts for Suzuki–Miyaura Coupling Processes: Scope
and Studies of the Effect of Ligand Structure. J. Am. Chem.
Soc. 2005, 127, 4685–4696.
(12) Pan, J.; Su, M.; Buchwald, S. L. Palladium(0)-Catalyzed
Intermolecular Amination of Unactivated Csp3–H Bonds.
Angew. Chem. Int. Ed. 2011, 50, 8647–8651.
(13) Tan, B.; Bai, L.; Ding, P.; Liu, J.; Wang, Y.; Luan, X.
Palladium-Catalyzed Intermolecular [4+1] Spiroannulation by
C(sp3)–H Activation and Naphthol Dearomatization. Angew.
Chem. Int. Ed. 2019, 58, 1474–1478.
(14) Rocaboy, R.; Anastasiou, I.; Baudoin, O. Redox-Neutral
Coupling between Two C(sp3)–H Bonds Enabled by 1,4-
Palladium Shift for the Synthesis of Fused Heterocycles.
Angew. Chem. Int. Ed. 2019, 58, 14625–14628.
(5) Giri, R.; Wasa, M.; Breazzano, S. P.; Yu, J.-Q. Converting
gem-Dimethyl Groups into Cyclopropanes via Pd-Catalyzed
Sequential C−H Activation and Radical Cyclization. Org.
Lett. 2006, 8, 5685–5688.
(6) (a) Liron, F.; Knochel, P. Reactivity of Stable Neopentyl-Pd
Intermediates in the Absence of Nucleophile. Tetrahedron
Lett. 2007, 48, 4943–4946. (b) Kim, H. S.; Gowrisankar, S.;
Kim, S. H.; Kim, J. N. Synthesis of 6-
Oxacyclopropa[a]indene Derivatives Starting from Baylis-
Hillman Adducts via Pd-Mediated C(sp3)–H Activation.
Tetrahedron Lett. 2008, 49, 3858–3861. (c) Huang, Q.;
Larock, R. C. Synthesis of Cyclopropanes by Pd-Catalyzed
Activation of Alkyl C–H Bonds. Tetrahedron Lett. 2009, 50,
7235–7238. (d) Mao, J.; Zhang, S.-Q.; Shi, B.-F.; Bao, W.
(15) Chaumontet, M.; Piccardi, R.; Audic, N.; Hitce, J.; Peglion,
J.-L.; Clot, E.; Baudoin, O. Synthesis of Benzocyclobutenes
by Palladium-Catalyzed C–H Activation of Methyl Groups:
Method and Mechanistic Study. J. Am. Chem. Soc. 2008, 130,
15157–15166.
(16) Gutiérrez-Bonet, Á.; Juliá-Hernández, F.; de Luis, B.; Martin,
R. Pd-Catalyzed C(sp3)–H Functionalization/Carbenoid
Insertion: All Carbon Quaternary Centers via Multiple C–C
Bond Formation. J. Am. Chem. Soc. 2016, 138, 6384–6387.
(17) (a) Lafrance, M.; Gorelsky, S. I.; Fagnou, K. High-Yielding
Palladium-Catalyzed Intramolecular Alkane Arylation:ꢀ
Reaction Development and Mechanistic Studies. J. Am.
Chem. Soc. 2007, 129, 14570–14571. (b) Kefalidis, C. E.;
Baudoin, O.; Clot, E. DFT Study of the Mechanism of
Benzocyclobutene Formation by Palladium-Catalysed C(sp3)–
H Activation: Role of the Nature of the Base and the
Phosphine. Dalton Trans. 2010, 39, 10528–10535. (c)
Rousseaux, S.; Gorelsky, S. I.; Chung, B. K. W.; Fagnou, K.
Investigation of the Mechanism of C(sp3)–H Bond Cleavage
in Pd(0)-Catalyzed Intramolecular Alkane Arylation Adjacent
to Amides and Sulfonamides. J. Am. Chem. Soc. 2010, 132,
10692–10705. (d) Rousseaux, R.; Davi, M.; Sofack-Kreutzer,
J.; Pierre, C.; Kefalidis, C. E.; Clot, E.; Fagnou, K.; Baudoin,
O. Intramolecular Palladium-Catalyzed Alkane C–H
Arylation from Aryl Chlorides. J. Am. Chem. Soc. 2010, 132,
10706–10716. (e) Kefalidis, C. E.; Davi, M.; Holstein, P. M.;
Clot, E.; Baudoin, O. Mechanistic Study on the Selectivity of
Olefin versus Cyclobutene Formation by Palladium(0)-
Palladium(0)-Catalyzed
Cyclopropanation
of
Benzyl
Bromides via C(sp3)–H Bond Activation. Chem. Commun.
2014, 50, 3692–3694. (e) Du, W.; Gu, Q.; Li, Z.; Yang, D.
Palladium(II)-Catalyzed
Intramolecular
Tandem
Aminoalkylation via Divergent C(sp3)–H Functionalization. J.
Am. Chem. Soc. 2015, 137, 1130–1135. (f) Chung, D. S.; Lee,
J. S.; Ryu, H.; Park, J.; Kim, H.; Lee, J. H.; Kim, U B.; Lee,
W. K.; Baik, M.-H.; Lee, S.-g. Palladium-Catalyzed
Divergent Cyclopropanation by Regioselective Solvent-
Driven C(sp3)–H Bond Activation. Angew. Chem. Int. Ed.
2018, 57, 15460–15464.
(7) For the construction of cyclopropanes via C–C activation and
C(sp3)–H activation: Cao, J.; Chen, L.; Sun, F.-N.; Sun, Y.-L.;
Jiang, K.-Z.; Yang, K.-F.; Xu, Z.; Xu, L.-W. Pd-Catalyzed
Enantioselective
Cylopropanation of Cyclobutanones. Angew. Chem. Int. Ed.
2019, 58, 897–901.
Ring
Opening/Cross-Coupling
and
(8) (a) Ma, S.; Gu, Z. 1,4‐Migration of Rhodium and Palladium
in Catalytic Organometallic Reactions. Angew. Chem. Int. Ed.
2005, 44, 7512–7517. (b) Shi, F.; Larock, R. C. Remote C–H
Activation via Through-Space Palladium and Rhodium
Migrations. Top. Curr. Chem. 2010, 292, 123–164. (c)
ACS Paragon Plus Environment