Rh-Catalyzed Annulative Insertion of Terminal Olefin onto Pyridines

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Rh-Catalyzed Annulative Insertion of Terminal Olefin onto Pyridines via a C−H Activation Strategy Using Ethenesulfonyl Fluoride as Ethylene Provider Chen Li and Hua-Li Qin* State Key Laboratory of Silicate Materials for Architectures; and School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan, Hubei Province 430070, P.R. China Downloaded via BUFFALO STATE on July 26, 2019 at 04:27:53 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

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ABSTRACT: A Rh(III)-catalyzed annulative insertion of ethylene onto picolinamides was achieved, providing a portal to a class of unique pyridine-containing molecules bearing a terminal olefin moiety for diversification. Application of this method for modification of Sorafenib was also accomplished.

P

picolinamide as a directing group for C−H bonds functionalization has been emerging as a new portal to pyridinecontaining molecules.8 In fact, Rh(III)-catalyzed olefination/ annulation of picolinamides has been proven to be a highly efficient method,9 whereas installing an ethylene moiety onto pyridine rings still remains untouched. The ethylene functionality is an abundant feedstock for organic synthesis;10 therefore, installing an ethylene onto the pyridine rings will provide a versatile handle for manipulation of pyridine-containing compounds to access libraries of pyridine cores for accelerating drug discovery progress.11 Ethenesulfonyl fluoride (ESF)12 is sensitive to nucleophilic solvents, bases, and nucleophiles. In addition, ESF is very likely to polymerize upon being heated. However, most of the C−H bond functionalization requires bases and/or elevated temperatures, which makes the coupling reactions of C−H bonds with ESF much more challenging. Herein, we described a Rh(III)-catalyzed annulative insertion of ethylene onto picolinamides for accessing to a series of unique pyridine-containing molecules bearing a terminal olefin functionality using ESF as a free ethylene provider (Scheme 1). Initially, we tested the reaction of readily available 2picolinamide (1a) and ESF (2) using 5 mol % of [Cp*RhCl2]2 as catalyst and 2 equiv of AgOAc as oxidant in 1,2-

yridine moieties are ubiquitously found as key motifs in agrochemicals, natural products, functional materials, ligands, catalysts, and small molecule therapeutics.1 Substituted pyridines were ranked the most common heterocycles in medicinal chemistry and pharmaceutical industry because of their diverse biological activities.2 Indeed, pyridine motifs are present in more than 100 FDA approved drugs including those blockbuster drugs of omeprazole (Prilosec), loratadine (Claritin), imatinib (Gleevec), and sorafenib (Nexavar), as illustrated in Figure 1.3

Figure 1. Representative blockbuster drugs containing pyridine moieties.

Picolinamides (2-pyridinecarboxamide) are a class of very important pyridine derivatives with unique properties for drug discovery and ligand development.4 The development of general, efficient, mild, and reliable methods for the construction of pyridines and picolinamides has been considered as a very significant target for the organic chemistry community.5 However, the electron-deficient property and strong Lewis basicity have resulted in the relatively low reactivity of pyridines rings, which has made it difficult to construct and diversify pyridine-containing molecules, including picolinamdes.6 On the other hand, transition-metalcatalyzed C−H bond functionalization has become a powerful tool for organic synthesis, medicinal chemistry, and material sciences in a step and atom-economical manner.7 The use of © 2019 American Chemical Society

Scheme 1. Rh(III)-Catalyzed Annulative Insertion of Ethylene onto Picolinamides

Received: April 18, 2019 Published: June 12, 2019 4495

DOI: 10.1021/acs.orglett.9b01364 Org. Lett. 2019, 21, 4495−4499

Letter

Organic Letters dichloroethane (DCE) at 130 °C; fortunately, a small amount of desired product 3a was obtained (Table 1, entry 1). In order

atmosphere, which indicated that oxygen might facilitate the conversion of 1a (Table 1, entries 8−10). It is worth noting that the 5 mol % loading Rh catalyst was essential to ensure the complete transformation of starting material because a significantly decreased yield of 3a was obtained when 2 mol % catalyst was used (Table 1, entry 11). Further control experiments showed that both the Rh catalyst and copper oxidant were necessary for this transformation (Table 1, entries 12 and 13). Remarkably, reducing the reaction time from 24 to 12 h successfully improved the yield of 3a from 83% to 93%, which may be attributed to the instability of the terminal olefin to undergo various possible side reactions at high temperature. (Table 1, entry 14). Therefore, the conditions of Table 1, entry 14, were chosen as standard procedure for further examination of substrate scope and functional group compatibility. With these optimized conditions in hand, we subsequently explored the substrate scope and limitations of this Rh(III)catalyzed annulative insertion of ethylene onto picolinamides 1. As shown in Scheme 2, it was pleasing to find that

Table 1. Screening Conditions for the Rh(III)-Catalyzed Reaction of Picolinamide and Ethenesulfonyl Fluoridea

entry 1 2 3 4 5 6 7 8 9c 10d 11e f

12

13 14g

temp (°C)

yieldb (3a, %)

/ / /

130 130 130

trace 16 33

AgSbF6 (20)

130

58

AgSbF6 (20)

120

83

AgSbF6 (20)

110

63

AgSbF6 (20)

120

62

AgSbF6 (20)

120

80

AgSbF6 (20)

120

75

AgSbF6 (20)

120

80

AgSbF6 (20)

120

55

AgSbF6 (20)

120

trace

AgSbF6 (20) AgSbF6 (20)

120 120

trace 93

AgSbF6 (Y mol %)

oxidant (X equiv) AgOAc (2.0) Cu(OAc)2 (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (1.5) Cu(OAc)2·H2O (2.5) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) Cu(OAc)2·H2O (2.0) / Cu(OAc)2·H2O (2.0)

Scheme 2. Scope Examination of Rh(III)-Catalyzed Annulationa

a

Reaction conditions: mixture of 1a (0.2 mmol), 2 (0.4 mmol, 2 equiv), [Cp*RhCl2]2 (5 mol %), oxidant, and DCE (0.1 M) was reacted at a corresponding temperature for 24 h under air atmosphere. b The yield was determined by HPLC using 3a as the external standard (tR = 3.79 min, λmax = 251.2 nm, acetonitrile/water = 70:30 (v/v)). cUnder argon atmosphere. dUnder oxygen atmosphere. e Using 2 mol % of [Cp*RhCl2]2. fWithout [Cp*RhCl2]2. gThe reaction was run for 12 h.

to improve the yield of 3a, a series of oxidants was surveyed. Delightedly, the use of 2 equiv of Cu(OAc)2 or Cu(OAc)2· H2O furnished the product 3a in 16% and 33% yield, respectively (Table 1, entries 2 and 3), while other commonly used oxidants provided the final product 3a in undetectable level (see the Supporting Information (SI) for details). Interestingly, the addition of AgSbF6 (20 mol %) as cocatalyst gave a significant improved yield of 58% (Table 1, entry 4). Encouraged by this result, we next turned to exploration of the influence of solvents, and the results indicated DCE was the best choice. Decreasing the reaction temperature to 120 °C afforded a dramatically increased yield of 83% (Table 1, entry 5), while further reducing the temperature to 110 °C led to a significant decreasing yield of 3a (63%, Table 1, entry 6). The amount of Cu(OAc)2·H2O loading was also investigated, and 2 equiv Cu(OAc)2·H2O was found to provide the best yield (Table 1, entries 5, 7, and 8). Performing the reaction under an oxygen atmosphere or air atmosphere generated slightly higher yields of 3a compared to that conducted under argon

a

Reaction conditions: mixture of 1 (1.0 mmol, 1 equiv), 2 (2.0 mmol, 2 equiv), [Cp*RhCl2]2 (5 mol %), AgSbF6 (20 mol %), Cu(OAc)2· H2O (2 equiv), and DCE (0.1 M) was reacted at 120 °C for 12 h under air atmosphere. bIsolated yields. cThe reaction was run for 18 h. d The reaction was conducted on a 10 mmol scale (1h, 1.78 g). 4496

DOI: 10.1021/acs.orglett.9b01364 Org. Lett. 2019, 21, 4495−4499

Letter

Organic Letters picolinamides (1) bearing both electron-donating and electron-withdrawing groups at different positions of the pyridine rings afforded their corresponding products 3 in moderate to high isolated yields (3a−3f, 43−93%). The X-ray structure of 3c in Scheme 2 clearly showed the formation of the pyrido pyrrolone skeleton bearing a terminal olefin moiety. N-substitution of the amides with either alkyl groups (1a−1o) or aryl groups (1p−1z) were smoothly transformed to their corresponding products 3a−3o or 3p−3z using this method. Notably, N-butylquinoline-2-carboxamide (1g), a polycyclic substrate, was also converted to the corresponding annulative product 3g with relatively lower yield compared to its monocyclic counterparts. Remarkably, the efficiency of annulative insertion ethylene to N-sec-butylpicolinamide (1h) was not deteriorated when the reaction was performed on a 10 mmol (1.78 g) scale, furnishing the corresponding product 3h in 75% isolated yield. Much to our delight, benzyl Nsubstituted and heterocycle N-substituted picolinamides afforded the desired products 3m and 3n in good yields, respectively. The conversion of N-(4-bromophenethyl)picolinamide 1o to its annulative product 3o was also accomplished smoothly in 62% yield, leaving a bromine atom intact for further transformations. Subsequent examination of substrate scope was expended to N-aryl-substituted picolinamides, which revealed that regardless of whether electron-rich or electron-deficient or the steric hindrance of substitutions on the aryl rings of amides (1p−1z), the efficiency of the desired transformation was not obviously affected. Furthermore, nicotinic acid and isonicotinic acid derivatives (1aa and 1ab) were examined under the standard reaction conditions; however, their corresponding products (3aa and 3ab) were not generated. Interestingly, the use of the benzamide (1ac) afforded a mixture of products 3ac (29% yield) and 3ad (35% yield) after reaction with ESF under the standard reaction conditions without formation of the corresponding terminal olefins. As depicted in Scheme 3, the utility of our products was demonstrated. The terminal olefin skeleton of compound 3v

was subjected to modification as illustrated in Scheme 4. Unsurprisingly, the corresponding product (11) was smoothly obtained under the developed conditions in moderate yield. Scheme 4. Modification of Sorafenib Using the Developed Method

A plausible mechanism for the reaction of Rh(III)-catalyzed annulative insertion of ethylene onto picolinamide 1 was proposed in Scheme 5. Rhodation of picolinamide 1 with Scheme 5. Plausible Mechanism

[Cp*RhCl2]2 produced the five-membered rhodacycle intermediate A, which was followed by an olefin insertion to generate the seven membered ring B. The intermediate B underwent a β-hydride elimination to provide the orthoolefinated intermediate C as an excellent Michael acceptor. The subsequent intramolecular Michael addition furnished a five-membered amide D, which went through an oxidative electron-transfer process to generate the iminium intermediate E. The hydrolysis of sulfonyl fluoride and the following elimination of SO3 provided the desired terminal olefin product 3. Because the intermediate D was not isolatable from the reaction, a similar analogue 3ae was synthesized from the reaction of benzamide (1ae) and ESF for investigating desufonylation mechanism (Scheme 6). The experimental results revealed that 3ae was completely transformed to the corresponding terminal olefin 3af in the presence of pyridine and copper oxidant, while without the presence of pyridine the desufonylation did not occur. Because the picolonamide moiety possesses a pyridine functionality, it was very likely

Scheme 3. Late-Stage Transformations of Terminal Olefin Moieties of Products 3

Scheme 6. Desufonylation Study was subjected to an oxidation to form the pyridine-fused phthalimide product 3va in excellent yield using KMnO4 as oxidant.13 The terminal olefin of 3c was highly functionalized to an acetal 3ca.14 Interestingly, m-CPBA-mediated oxidation of annulative product 3f led to the formation of a mixture of imide 3fa and epoxypropane analogue 3fb in about a 1.1:1.0 ratio.15 To apply this method for modification of complicated molecules, the FDA-approved drug sorafenib (10), a very important Raf kinase inhibitor for the treatment of cancer,16 4497

DOI: 10.1021/acs.orglett.9b01364 Org. Lett. 2019, 21, 4495−4499

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Organic Letters

(2) (a) Mitscher, L. A. Bacterial Topoisomerase Inhibitors: Quinolone and Pyridone Antibacterial Agents. Chem. Rev. 2005, 105, 559. (b) Jones, G. In Comprehensive Heterocyclic Chemistry II; Katritzky, A. R., Rees, C. W., Scriven, E. F. V., McKillop, A., Eds.; Pergamon: Oxford, 1996; Vol. 5, p 167. (3) (a) Li, J. J. Heterocyclic Chemistry in Drug Discovery; John Wiley & Sons: Hoboken, NJ, 2013. (b) Goetz, A. E.; Garg, N. K. Regioselective reactions of 3,4-pyridynes enabled by the aryne distortion model. Nat. Chem. 2013, 5, 54. (c) Vitaku, E.; Smith, D. T.; Njardarson, J. T. Analysis of the Structural Diversity, Substitution Patterns, and Frequency of Nitrogen Heterocycles among U.S. FDA Approved Pharmaceuticals. J. Med. Chem. 2014, 57, 10257. (4) (a) Sigel, H.; Martin, R. B. Coordinating properties of the amide bond. Stability and structure of metal ion complexes of peptides and related ligands. Chem. Rev. 1982, 82, 385. (b) Moku, B.; Ravindar, L.; Rakesh, K. P.; Qin, H.-L. The significance of N-methylpicolinamides in the development of anticancer therapeutics: Synthesis and structure-activity relationship (SAR) studies. Bioorg. Chem. 2019, 86, 513. (5) For selected reviews, see: (a) Bull, J. A.; Mousseau, J. J.; Pelletier, G.; Charette, A. B. Synthesis of Pyridine and Dihydropyridine Derivatives by Regio- and Stereoselective Addition to N-Activated Pyridines. Chem. Rev. 2012, 112, 2642. (b) Gulevich, A. V.; Dudnik, A. S.; Chernyak, N.; Gevorgyan, V. Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles. Chem. Rev. 2013, 113, 3084. (c) Allais, C.; Grassot, J. M.; Rodriguez, J.; Constantieux, T. Metal-Free Multicomponent Syntheses of Pyridines. Chem. Rev. 2014, 114, 10829. (6) (a) Eicher, T.; Hauptmann, S.; Speicher, A. The Chemistry of Heterocycles, 3rd ed.; Wiley-VCH, 2012. (b) Joule, J. A.; Mills, K. Heterocyclic Chemistry, 4th ed.; Blackwell Publishing: Oxford, 2000. (7) For selected reviews, see: (a) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Rhodium-Catalyzed C−C Bond Formation via Heteroatom-Directed C−H Bond Activation. Chem. Rev. 2010, 110, 624. (b) Lyons, T. W.; Sanford, M. S. Palladium-Catalyzed LigandDirected C−H Functionalization Reactions. Chem. Rev. 2010, 110, 1147. (c) Davies, H. M. L.; Du Bois, J.; Yu, J.-Q. C−H Functionalization in organic synthesis. Chem. Soc. Rev. 2011, 40, 1855. (d) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Ruthenium(II)-Catalyzed C−H Bond Activation and Functionalization. Chem. Rev. 2012, 112, 5879. (e) Zhang, F.; Spring, D. R. Arene C−H functionalisation using a removable/modifiable or a traceless directing group strategy. Chem. Soc. Rev. 2014, 43, 6906. (8) For representative examples, see: (a) Zaitsev, J. V. G.; Shabashov, D.; Daugulis, O. Highly Regioselective Arylation of sp3 C−H Bonds Catalyzed by Palladium Acetate. J. Am. Chem. Soc. 2005, 127, 13154. (b) Xu, J.-W.; Zhang, J.-J.; Rao, W.- H.; Shi, B.-F. SiteSelective Alkenylation of δ-C(sp3)−H Bonds with Alkynes via a SixMembered Palladacycle. J. Am. Chem. Soc. 2016, 138, 10750. (c) Liu, Z.; Derosa, J.; Engle, K. M. Palladium(II)-Catalyzed Regioselective syn-Hydroarylation of Disubstituted Alkynes Using a Removable Directing Group. J. Am. Chem. Soc. 2016, 138, 13076. (d) Shang, R.; Ilies, L.; Nakamura, E. Iron-Catalyzed Directed C(sp2)−H and C(sp3)−H Functionalization with Trimethylaluminum. J. Am. Chem. Soc. 2015, 137, 7660. (e) Takamatsu, K.; Hirano, K.; Miura, M. Copper-Mediated Decarboxylative Coupling of Benzamides with ortho-Nitrobenzoic Acids by Directed C−H Cleavage. Angew. Chem., Int. Ed. 2017, 56, 5353. (f) Roane, J.; Daugulis, O. Copper-Catalyzed Etherification of Arene C−H Bonds. Org. Lett. 2013, 15, 5842. (g) Lan, J.; Xie, H.; Lu, X.; Deng, Y.; Jiang, H.; Zeng, W. Co(II)Catalyzed Regioselective Cross-Dehydrogenative Coupling of Aryl C−H Bonds with Carboxylic Acids. Org. Lett. 2017, 19, 4279. (h) Grigorjeva, L.; Daugulis, O. Cobalt-Catalyzed, AminoquinolineDirected C(sp2)-H Bond Alkenylation by Alkynes. Angew. Chem., Int. Ed. 2014, 53, 10209. (9) (a) Martínez, Á . M.; Rodríguez, N.; Arrayás, R. G.; Carretero, J. C. Synthesis of alkylidene pyrrolo[3,4-b]pyridin-7-one derivatives via RhIII -catalyzed cascade oxidative alkenylation/annulation of picolinamides. Chem. Commun. 2014, 50, 6105. (b) Cai, S.; Chen, C.; Shao,

that the picolonamide also served as a special base to promote the desufonylation of intermediate D to generate terminal olefin 3. In summary, we have developed a Rh(III)-catalyzed annulative method for insertion of ethylene onto picolinamides providing a portal to a class of unique pyridine-containing molecules bearing a terminal olefin for manipulations. In addition, diversifications of the terminal olefin moieties of the new molecules, such as oxidation and epoxidation, were also evaluated. The utilization of this method for late-stage modification of the drug sorafenib was achieved. Further studies on the bioactivities of the constructed new compounds are ongoing in our laboratory.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.orglett.9b01364. General methods, synthetic procedures, and characterization (PDF) Accession Codes

CCDC 1905736 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Hua-Li Qin: 0000-0002-6609-0083 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to the National Natural Science Foundation of China (Grant No. 21772150), the Wuhan Applied Fundamental Research Plan of Wuhan Science and Technology Bureau (Grant No. 2017060201010216), the 111 Project (No. B18038), and Wuhan University of Technology for the financial support.

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REFERENCES

(1) (a) Pozharskii, A. F.; Soldatenkov, A.; Katritzky, A. R. Heterocycles in Life and Society: An Introduction to Heterocyclic Chemistry, Biochemistry, and Applications, 2nd ed.; John Wiley & Sons, 2011. (b) Joule, J. A.; Mills, K. Heterocyclic Chemistry, 5th ed.; John Wiley & Sons, 2010. (c) Roughley, S. D.; Jordan, A. M. The Medicinal Chemist’s Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates. J. Med. Chem. 2011, 54, 3451. (d) Su, S. J.; Chiba, T.; Takeda, T.; Kido, J. Pyridine-Containing Triphenylbenzene Derivatives with High Electron Mobility for Highly Efficient Phosphorescent OLEDs. Adv. Mater. 2008, 20, 2125. (e) Zafar, M. N.; Atif, A. H.; Nazar, M. F.; Sumrra, S. H.; Saba, G. E.; Paracha, R. Pyridine and related ligands in transition metal homogeneous catalysis. Russ. J. Coord. Chem. 2016, 42, 1. (f) Michael, J. P. Quinoline, quinazoline and acridone alkaloids. Nat. Prod. Rep. 2005, 22, 627. 4498

DOI: 10.1021/acs.orglett.9b01364 Org. Lett. 2019, 21, 4495−4499

Letter

Organic Letters P.; Xi, C. Rh(III)-Catalyzed Cascade Oxidative Olefination/ Cyclization of Picolinamides and Alkenes via C−H Activation. Org. Lett. 2014, 16, 3142. (c) Zhou, J.; Li, B.; Qian, Z.-C.; Shi, B.-F. Rhodium(III)-Catalyzed Oxidative Olefination of Picolinamides: Convenient Synthesis of 3-Alkenylpicolinamides. Adv. Synth. Catal. 2014, 356, 1038. (d) Presset, M.; Oehlrich, D.; Rombouts, F.; Molander, G. A. Complementary Regioselectivity in Rh(III)Catalyzed Insertions of Potassium Vinyltrifluoroborate via C−H Activation: Preparation and Use of 4-Trifluoroboratotetrahydroisoquinolones. Org. Lett. 2013, 15, 1528. (e) Zhou, J.; Li, B.; Hu, F.; Shi, B.-F. Rhodium(III)-Catalyzed Oxidative Olefination of Pyridines and Quinolines: Multigram-Scale Synthesis of Naphthyridinones. Org. Lett. 2013, 15, 3460. (f) Wei, X. H.; Wang, F.; Song, G. Y.; Du, Z. Y.; Li, X. W. Rhodium(III)-catalyzed oxidative mono- and di-olefination of isonicotinamides. Org. Biomol. Chem. 2012, 10, 5521. (g) Qian, Z.C.; Zhou, J.; Li, B.; Hu, F.; Shi, B.-F. Rh(III)-catalyzed regioselective hydroarylation of alkynes via directed C−H functionalization of pyridines. Org. Biomol. Chem. 2014, 12, 3594. (10) (a) Saini, V.; Stokes, B. J.; Sigman, M. S. Transition-MetalCatalyzed Laboratory-Scale Carbon−Carbon Bond-Forming Reactions of Ethylene. Angew. Chem., Int. Ed. 2013, 52, 11206. (b) Harper, M. J.; Emmett, E. J.; Bower, J. F.; Russell, C. A. Oxidative 1,2Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation. J. Am. Chem. Soc. 2017, 139, 12386. (c) Bayeh, L.; Le, P. Q.; Tambar, U. K. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block. Nature 2017, 547, 196. (11) (a) Brown, N. Scaffold Hopping in Medicinal Chemistry; WileyVCH: Weinheim, 2013. (b) Hajduk, P. J.; Galloway, W. R. J. D.; Spring, D. R. A question of library design. Nature 2011, 470, 42. (c) Galloway, W. R. J. D.; Isidro-Llobet, A.; Spring, D. R. Diversityoriented synthesis as a tool for the discovery of novel biologically active small molecules. Nat. Commun. 2010, 1, 80. (d) Tan, D. S. Diversity-oriented synthesis: exploring the intersections between chemistry and biology. Nat. Chem. Biol. 2005, 1, 74. (e) Schreiber, S. L. Target-oriented and diversity-oriented organic synthesis in drug discovery. Science 2000, 287, 1964. (12) (a) Dong, J.; Krasnova, L.; Finn, M. G.; Sharpless, K. B. Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry. Angew. Chem., Int. Ed. 2014, 53, 9430. (b) Zheng, Q.; Dong, J.; Sharpless, K. B. Ethenesulfonyl Fluoride (ESF): An OnWater Procedure for the Kilogram-Scale Preparation. J. Org. Chem. 2016, 81, 11360. (c) Qin, H.-L.; Zheng, Q.; Bare, G. A. L.; Wu, P.; Sharpless, K. B. A Heck−Matsuda Process for the Synthesis of βArylethenesulfonyl Fluorides: Selectively Addressable Bis-electrophiles for SuFEx Click Chemistry. Angew. Chem., Int. Ed. 2016, 55, 14155. (d) Chinthakindi, P. K.; Govender, K. B.; Kumar, A. S.; Kruger, H. G.; Govender, T.; Naicker, T.; Arvidsson, P. I. A Synthesis of “Dual Warhead” β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams. Org. Lett. 2017, 19, 480. (e) Zha, G.-F.; Bare, G. A. L.; Leng, J.; Shang, Z.-P.; Luo, Z.; Qin, H.-L. Gram-Scale Synthesis of β-(Hetero) arylethenesulfonyl Fluorides via a Pd(OAc)2 Catalyzed Oxidative Heck Process with DDQ or AgNO3 as an Oxidant. Adv. Synth. Catal. 2017, 359, 3237. (f) Smedley, C. J.; Giel, M.-C.; Molino, A.; Barrow, A. S.; Wilson, D. J. D.; Moses, J. E. 1Bromoethene-1-sulfonyl fluoride (BESF) is another good connective hub for SuFEx click chemistry. Chem. Commun. 2018, 54, 6020. (g) Leng, J.; Qin, H. -L. 1-Bromoethene-1-sulfonyl fluoride (1-BrESF), a new SuFEx clickable reagent, and its application for regioselective construction of 5-sulfonylfluoro isoxazoles. Chem. Commun. 2018, 54, 4477. (h) Wang, S.-M.; Li, C.; Leng, J.; Bukhari, S. N. A.; Qin, H.-L. Rhodium(III)-catalyzed Oxidative Coupling of N-Methoxybenzamides and Ethenesulfonyl fluoride: a C−H Bond Activation Strategy for the Preparation of 2-Aryl ethenesulfonyl fluorides and Sulfonyl fluoride Substituted γ-Lactams. Org. Chem. Front. 2018, 5, 1411. (i) Li, C.; Wang, S.-M.; Qin, H.-L. A Rh-Catalyzed Air and Moisture Tolerable Aldehyde (Ketone)Directed Fluorosulfonylvinylation of Aryl C(sp2)−H Bonds. Org. Lett. 2018, 20, 4699. (j) Wang, S.-M.; Moku, B.; Leng, J.; Qin, H.-L. Rh-Catalyzed Carboxylates Directed C−H Activation for the

Synthesis of ortho-Carboxylic 2-Arylethenesulfonyl Fluorides: Access to Unique Electrophiles for SuFEx Click Chemistry. Eur. J. Org. Chem. 2018, 2018, 4407. (k) Ncube, G.; Huestis, M. P. Directed Cp*RhIIICatalyzed Fluorosulfonylvinylation of Arenes. Organometallics 2019, 38, 76. (l) Chen, X.-Y.; Wu, Y.-C.; Zhou, J.; Wang, P.; Yu, J.-Q. Synthesis of β-Arylethenesulfonyl Fluoride via Pd-Catalyzed Nondirected C−H Alkenylation. Org. Lett. 2019, 21, 1426. (m) Liu, M.; Yang, P.; Karunananda, K. M.; Wang, Y.; Liu, P.; Engle, K. M. C(alkenyl)−H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis. J. Am. Chem. Soc. 2018, 140, 5805. (13) Huo, X.; Quan, M.; Yang, G.; Zhao, X.; Liu, D.; Liu, Y.; Zhang, W. Hydrogen-Bond-Activated Palladium-Catalyzed Allylic Alkylation via Allylic Alkyl Ethers: Challenging Leaving Groups. Org. Lett. 2014, 16, 1570. (14) Kang, B.-Y.; Gade, L. H. The Nature of the Catalytically Active Species in Olefin Dioxygenation with PhI(OAc)2: Metal or Proton? J. Am. Chem. Soc. 2011, 133, 3658. (15) Qian, H.; Zhao, W.; Wang, Z.; Sun, J. Organocatalytic Enantioand Diastereoselective Synthesis of 1,2-Dihydronaphthalenes from Isobenzopyrylium Ions. J. Am. Chem. Soc. 2015, 137, 560. (16) (a) Bankston, D.; Dumas, J.; Natero, R.; Riedl, B.; Monahan, M. K.; Sibley, R. A Scaleable Synthesis of BAY 43−9006: A Potent Raf Kinase Inhibitor for the Treatment of Cancer. Org. Process Res. Dev. 2002, 6, 777. (b) Sonoshita, M.; Scopton, A. P.; Ung, P. M. U.; Murray, M. A.; Silber, L.; Maldonado, A. Y.; Real, A.; Schlessinger, A.; Cagan, R. L.; Dar, A. C. A whole-animal platform to advance a clinical kinase inhibitor into new disease space. Nat. Chem. Biol. 2018, 14, 291.

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