1. Selected reviews on chemoselectivity. (a) Boudier, A.; Bromm, L. O.; Lotz, M.; Knochel, P. New Applications of Polyfunctional Organometallic Compounds in Organic Synthesis. Angew. Chem. Int. Ed. 2000, 39, 4414–4435. (b) Shenvi, R. A.; O’Malley, D. P.; Baran, P. S. Chemoselectivity: The Mother of Invention in Total Synthesis. Acc. Chem. Res. 2009, 42, 530–541. (c) Afagh, N. A.; Yudin, A. K. Chemoselectivity and the Curious Reactivity Preferences of Functional Groups. Angew. Chem. Int. Ed. 2010, 49, 262–310.
2. The list of selected reviews on nucleophilic addition to amides (a) Seebach, D. Generation of Secondary, Tertiary, and Quaternary Centers by Geminal Disubstitution of Carbonyl Oxygens. Angew. Chem. Int. Ed. 2011, 50, 96–101. (b) Pace, V.; Holzer, W. Chemoselective Activation Strategies of Amidic Carbonyls towards Nucleophilic Reagents. Aust. J. Chem. 2013, 66, 507–510. (c) Sato, T.; Chida, N. Nucleophilic Addition to N-Alkoxyamides. Org. Biomol. Chem. 2014, 12, 3147–3150. (d) Pace, V.; Holzer, W.; Olofsson, B. Increasing the Reactivity of Amides towards Organometallic Reagents: An Overview. Advanced Synthesis & Catalysis, 2014, 356, 3697–3736. (e) Volkov, A.; Tinnis, F.; Slagbrand, T.; Trillo, P.; Adolfsson, H. Chemoselective Reduction of Carboxamides. Chem. Soc. Rev. 2016, 45, 6685–6697. (f) Kaiser, D.; Maulide, N. Making the Least Reactive Electrophile the First in Class: Domino Electrophilic Activation of Amides. J. Org. Chem. 2016, 81, 4421–4428. (g) Sato, T.; H.; Chida. Nucleophilic Addition to N─Alkoxyamides: Development and Application to the Total Synthesis of Gephyrotoxin. J. Synth. Org. Chem., Jpn., 2016, 74, 599–610 (h) Więcław, M. M.; Stecko, S. Hydrozirconation of C=X Functionalities with Schwartz’s Reagent. Euro. J. Org. Chem. 2018, 2018, 6601–6623. (i) Chardon, A.; Morisset, E.; Rouden, J.; Blanchet, J. Recent Advances in Amide Reductions. Synthesis 2018, 50, 984–997. (j) Sato, T.; Yoritate, M.; Tajima, H.; Chida, N. Total Synthesis of Complex Alkaloids by Nucleophilic Addition to Amides. Org. Biomol. Chem. 2018, 16, 3864–3875.
3. Examples of nucleophlic addition to amides utilizing thioiminium salts. (a) Murai, T.; Mutoh, Y.; Ohta, Y.; Murakami, M. Synthesis of Tertiary Propargylamines by Sequential Reactions of in Situ Generated Thioiminium Salts with Organolithium and - Magnesium Reagents. J. Am. Chem. Soc. 2004, 126, 5968–5969. (b) Agosti, A.; Britto, S.; Renaud, P. An Efficient Method to Convert Lactams and Amides into 2,2-Dialkylated Amines. Org. Lett. 2008, 10, 1417–1420.
4. Xiao, K. J.; Luo, J. M.; Ye, K. Y.; Wang, Y.; Huang, P. Q. Direct, One-Pot Sequential Reductive Alkylation of Lactams/Amides with Grignard and Organolithium Reagents through Lactam/Amide Activation. Angew. Chem. Int. Ed. 2010, 49, 3037–3040.
5. Examples of reductive nucleophilic addition to amides with Schwartz’s reagent. (a) Oda, Y.; Sato, T.; Chida, N. Direct Chemoselective Allylation of Inert Amide Carbonyls. Org. Lett. 2012, 14, 950–953. (b) Nakajima, M.; Oda, Y.; Wada, T.; Minamikawa, R.; Shirokane, K.; Sato, T.; Chida, N. Chemoselective Reductive Nucleophilic Addition to Tertiary Amides, Secondary Amides, and N-Methoxyamides. Chem. Eur. J. 2014, 20, 17565–17571.
6. Nahm, S.; Weinreb, S. M. N-Methoxy-n-Methylamides as Effective Acylating Agents. Tetrahedron Lett. 1981, 22, 3815–3818.
7. Reduction of amides by Schwartz’s reagent. (a) Schedler, D. J. A.; Godfrey, A. G.; Ganem, B. Reductive Deoxygenation by Cp2ZrHCl: Selective Formation of Imines via Zirconation/Hydrozirconation of Amides. Tetrahedron Lett. 1993, 34, 5035–5038. (b) Schedler, D. J. A.; Li, J.; Ganem, B. Reduction of Secondary Carboxamides to Imines. J. Org. Chem. 1996, 61, 4115–4119.
8. Spletstoser, J. T.; White, J. M.; Tunoori, A. R.; Georg, G. I. Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp2Zr(H)Cl: Scope and Mechanistic Insight. J. Am. Chem. Soc. 2007, 129, 3408–3419.
9. Piper, T. S.; Lemal, D.; Wilkinson, G. A Silyliron Compound; an Fe-Si δ Bond. Naturwissenschaften 1956, 43, 129.
10. The list of selected reviews on hydrosilane transition metal complex. (a) Corey, J. Y. Reactions of Hydrosilanes with Transition Metal Complexes Characterization of the Products. Chem. Rev. 2011, 111, 863–1071. (b) Corey, J. Y. Reactions of Hydrosilanes with Transition Metal Complexes. Chem. Rev. 2016, 116, 11291–11435.
11. Selected reviews on hydrosilylation of amides. (a) Addis, D.; Das, S.; Junge, K.; Beller, M. Selective Reduction of Carboxylic Acid Derivatives by Catalytic Hydrosilylation. Angew. Chem. Int. Ed. 2011, 50, 6004–6011. (b) Zhang, M.; Zhang, A. Iron-Catalyzed Hydrosilylation Reactions. Appl. Organomet. Chem. 2010, 24, 751–757. (c) Werkmeister, S.; Junge, K.; Beller, M. Catalytic Hydrogenation of Carboxylic Acid Esters, Amides, and Nitriles with Homogeneous Catalysts. Org. Process Res. Dev. 2014, 18, 289–302. (d) Volkov, A.; Tinnis, F.; Slagbrand, T.; Trillo, P.; Adolfsson, H. Chemoselective Reduction of Carboxamides. Chem. Soc. Rev. 2016, 45, 6685–6697. (e) Kaiser, D.; Bauer, A.; Lemmerer, M.; Maulide, N. Amide Activation: An Emerging Tool for Chemoselective Synthesis. Chem. Soc. Rev. 2018, 47, 7899–7925. (f) Khalimon, A. Y.; Gudun, K. A.; Hayrapetyan, D. Base Metal Catalysts for Deoxygenative Reduction of Amides to Amines. Catalysts 2019, 9, 1–26. (g) Chardon, A.; Morisset, E.; Rouden, J.; Blanchet, J. Recent Advances in Amide Reductions. Synthesis 2018, 50, 984–997. (h) Iglesias, M.; Fernández-Alvarez, F. J.; Oro, L. A. Non-Classical Hydrosilane Mediated Reductions Promoted by Transition Metal Complexes. Coord. Chem. Rev. 2019, 386, 240–266. (i) Shaikh, N. S. Sustainable Amine Synthesis: Iron Catalyzed Reactions of Hydrosilanes with Imines, Amides, Nitroarenes and Nitriles. ChemistrySelect 2019, 4, 6753–6777.
12. Bower, S.; Kreutzer, K. A.; Buchwald, S. L. A Mild General Procedure for the One-Pot Conversion of Amides to Aldehydes. Angew. Chem. Int. Ed. 1996, 35, 1515–1516.
13. Selected example of hydrosilylation of tertiary amide to enamine using Vaska-type iridium catalyst. (a) Motoyama, Y.; Aoki, M.; Takaoka, N.; Aoto, R.; Nagashima, H. Highly Efficient Synthesis of Aldenamines from Carboxamides by Iridium-Catalyzed Silane-Reduction/Dehydration under Mild Conditions. Chem. Commun. 2009, 1574–1576. (b) Tahara, A.; Miyamoto, Y.; Aoto, R.; Shigeta, K.; Une, Y.; Sunada, Y.; Motoyama, Y.; Nagashima, H. Catalyst Design of Vaska-Type Iridium Complexes for Highly Efficient Synthesis of π-Conjugated Enamines. Organometallics 2015, 34, 4895–4907. (c) Une, Y.; Tahara, A.; Miyamoto, Y.; Sunada, Y.; Nagashima, H. Iridium-PPh3 Catalysts for Conversion of Amides to Enamines. Organometallics 2019, 38, 852–862. (d) Tahara, A.; Kitahara, I.; Sakata, D.; Kuninobu, Y.; Nagashima, H. Donor-Acceptor π- Conjugated Enamines: Functional Group Compatible Synthesis from Amides and Their Photoabsorption and Photoluminescence Properties. J. Org. Chem. 2019, 84, 15236-15254.
14. Yang, Z. P.; Lu, G. S.; Ye, J. L.; Huang, P. Q. Ir-Catalyzed Chemoselective Reduction of β-Amido Esters: A Versatile Approach to β-Enamino Esters. Tetrahedron 2019, 75, 1624–1631.
15. Selected example of semi-reduction of tertiary amides using Mo(CO)6. (a) Volkov, A.; Tinnis, F.; Slagbrand, T.; Pershagen, I.; Adolfsson, H. Mo(CO)6 Catalysed Chemoselective Hydrosilylation of α,β-Unsaturated Amides for the Formation of Allylamines. Chem. Commun. 2014, 50, 14508–14511. (b) Tinnis, F.; Volkov, A.; Slagbrand, T.; Adolfsson, H. Chemoselective Reduction of Tertiary Amides under Thermal Control: Formation of Either Aldehydes or Amines. Angew. Chem. Int. Ed. 2016, 55, 4562–4566.
16. Volkov, A.; Tinnis, F.; Adolfsson, H. Catalytic Reductive Dehydration of Tertiary Amides to Enamines under Hydrosilylation Conditions. Org. Lett. 2014, 16, 680–683.
17. Selected review of the mechanistic insights on hydrosilylation of carbonyl compounds (a) Riener, K.; Högerl, M. P.; Gigler, P.; Kühn, F. E. Rhodium-Catalyzed Hydrosilylation of Ketones: Catalyst Development and Mechanistic Insights. ACS Catal. 2012, 2, 613–621. (b) Iglesias, M.; Fernández-Alvarez, F. J.; Oro, L. A. Outer-Sphere Ionic Hydrosilylation Catalysis. ChemCatChem 2014, 6, 2486–2489. (c) Iglesias, M.; Fernández-Alvarez, F. J.; Oro, L. A. Non-Classical Hydrosilane Mediated Reductions Promoted by Transition Metal Complexes. Coord. Chem. Rev. 2019, 386, 240–266.
18. Ojima, I.; Nihonyanagi, M.; Nagai, Y. Rhodium Complex Catalysed Hydrosilylation of Carbonyl Compounds. J. Chem. Soc. Chem. Commun. 1972, 0, 938a–938a.
19. Ojima, I.; Nihonyanagi, M.; Kogure, T.; Kumagai, M.; Horiuchi, S.; Nakatsugawa, K.; Nagai, Y. Reduction of Carbonyl Compounds via Hydrosilylation. I. Hydrosilylation of Carbonyl Compounds Catalyzed by Tris(Triphenylphosphine)Chlororhodium. J. Organomet. Chem. 1975, 94, 449–461.
20. Ojima, I.; Kogure, T.; Nagai, Y. ASYMMETRIC REDUCTION OF KETONES VIA HYDROSILYLATION CATALYZED BY A RHODIUM(I) COMPLEX WITH CHIRAL PHOSPHINE LIGANDS. Chem. Lett. 1973, 2, 541–544.
21. Zheng, G. Z.; Chan, T. H. Regiocontrolled Hydrosilation of α,β-Unsaturated Carbonyl Compounds Catalyzed by Hydridotetrakis(Triphenylphosphine)Rhodium(I). Organometallics 1995, 14, 70–79.
22. Gade, L. H.; César, V.; Bellemin-Laponnaz, S. A Modular Assembly of Chiral Oxazolinylcarbene- Rhodium Complexes: Efficient Phosphane-Free Catalysts for the Asymmetric Hydrosilylation of Dialkyl Ketones. Angew. Chem. Int. Ed. 2004, 43, 1014–1017.
23. Schneider, N.; Finger, M.; Haferkemper, C.; Bellemin-Laponnaz, S.; Hofmann, P.; Gade, L. H. Metal Silylenes Generated by Double Silicon-Hydrogen Activation: Key Intermediates in the Rhodium-Catalyzed Hydrosilylation of Ketones. Angew. Chem. Int. Ed. 2009, 48, 1609–1613.
24. Schneider, N.; Finger, M.; Haferkemper, C.; Bellemin-Laponnaz, S.; Hofmann, P.; Gade, L. H. Multiple Reaction Pathways in Rhodium-Catalyzed Hydrosilylations of Ketones. Chem. Eur. J. 2009, 15, 11515–11529.
25. Gigler, P.; Bechlars, B.; Herrmann, W. A.; Kühn, F. E. Hydrosilylation with Biscarbene Rh(I) Complexes: Experimental Evidence for a Silylene-Based Mechanism. J. Am. Chem. Soc. 2011, 133, 1589–1596.
26. Parks, D. J.; Piers, W. E. Tris(Pentafluorophenyl)Boron-Catalyzed Hydrosilation of Aromatic Aldehydes, Ketones, and Esters. J. Am. Chem. Soc. 1996, 118, 9440–9441.
27. Rendler, S.; Oestreich, M. Conclusive Evidence for an SN2-Si Mechanism in the B(C6F5)3-Catalyzed Hydrosilylation of Carbonyl Compounds: Implications for the Related Hydrogenation. Angew. Chem. Int. Ed. 2008, 47, 5997–6000.
28. Park, S.; Brookhart, M. Hydrosilylation of Carbonyl-Containing Substrates Catalyzed by an Electrophilic Η1-Silane Iridium(III) Complex. Organometallics 2010, 29, 6057–6064.
29. Park, S.; Brookhart, M. Development and Mechanistic Investigation of a Highly Efficient Iridium(V) Silyl Complex for the Reduction of Tertiary Amides to Amines. J. Am. Chem. Soc. 2012, 134, 640–653.
30. Metsänen, T. T.; Hrobárik, P.; Klare, H. F. T.; Kaupp, M.; Oestreich, M. Insight into the Mechanism of Carbonyl Hydrosilylation Catalyzed by Brookharts Cationic Iridium(III) Pincer Complex. J. Am. Chem. Soc. 2014, 136, 6912–6915.
31. Zhao, L.; Nakatani, N.; Sunada, Y.; Nagashima, H.; Hasegawa, J. Y. Theoretical Study on the Rhodium-Catalyzed Hydrosilylation of C=C and C=O Double Bonds with Tertiary Silane. J. Org. Chem. 2019, 84, 8552–8561.
32. Gregory, A. W.; Chambers, A.; Hawkins, A.; Jakubec, P.; Dixon, D. J. Iridium-Catalyzed Reductive Nitro-Mannich Cyclization. Chem. Eur. J. 2015, 21, 111–114.
33. During the preparation of this dissertation, the group of Dixon independently reported the elegant reductive nucleophilic addition to tertiary amides using the Nagashima’s catalytic system, see: Fuentes de Arriba, Á. L.; Lenci, E.; Sonawane, M.; Formery, O.; Dixon, D. J. Iridium-Catalyzed Reductive Strecker Reaction for Late-Stage Amide and Lactam Cyanation. Angew. Chem. Int. Ed. 2017, 56, 3655–3659.
34. Xie, L. G.; Dixon, D. J. Tertiary Amine Synthesis: Via Reductive Coupling of Amides with Grignard Reagents. Chem. Sci. 2017, 8, 7492–7497.
35. Gabriel, P.; Xie, L.; Dixon, D. J. Iridium-Catalyzed Reductive Coupling of Grignard Reagents and Tertiary Amides. Org. Synth. 2019, 96, 511–527.
36. Xie, L. G.; Dixon, D. J. Iridium-Catalyzed Reductive Ugi-Type Reactions of Tertiary Amides. Nat. Commun. 2018, 9, 1–124.
37. Gabriel, P.; Gregory, A. W.; Dixon, D. J. Iridium-Catalyzed Aza-Spirocyclization of Indole-Tethered Amides: An Interrupted Pictet–Spengler Reaction. Org. Lett. 2019, 21, 6658–6662.
38. Huang, P. Q.; Ou, W.; Han, F. Chemoselective Reductive Alkynylation of Tertiary Amides by Ir and Cu(I) Bis-Metal Sequential Catalysis. Chem. Commun. 2016, 52, 11967–11970.
39. Hu, X. N.; Shen, T. L.; Cai, D. C.; Zheng, J. F.; Huang, P. Q. The Iridium-Catalysed Reductive Coupling Reaction of Tertiary Lactams/Amides with Isocyanoacetates. Org. Chem. Front. 2018, 5, 2051–2056.
40. Wang, S. R.; Huang, P. Q. Cross-Coupling of Secondary Amides with Tertiary Amides: The Use of Tertiary Amides as Surrogates of Alkyl Carbanions for Ketone Synthesis. Chinese J. Chem. 2019, 2015–2019.
41. Trillo, P.; Slagbrand, T.; Adolfsson, H. Straightforward α-Amino Nitrile Synthesis Through Mo(CO)6-Catalyzed Reductive Functionalization of Carboxamides. Angew. Chem. Int. Ed. 2018, 57, 12347–12351.
42. Trillo, P.; Slagbrand, T.; Tinnis, F.; Adolfsson, H. Facile Preparation of Pyrimidinediones and Thioacrylamides: Via Reductive Functionalization of Amides. Chem. Commun. 2017, 53, 9159– 9162.
43. Trillo, P.; Slagbrand, T.; Tinnis, F.; Adolfsson, H. Mild Reductive Functionalization of Amides into N-Sulfonylformamidines. ChemistryOpen 2017, 6, 484–487.
44. Jakubec, P.; Hawkins, A.; Felzmann, W.; Dixon, D. J. Total Synthesis of Manzamine A and Related Alkaloids. J. Am. Chem. Soc. 2012, 134, 17482–17485.
45. Tan, P. W.; Seayad, J.; Dixon, D. J. Expeditious and Divergent Total Syntheses of Aspidosperma Alkaloids Exploiting Iridium(I)-Catalyzed Generation of Reactive Enamine Intermediates. Angew. Chem. Int. Ed. 2016, 55, 13436–13440.
46. Takahashi, Y.; Sato, T.; Chida, N. Iridium-Catalyzed Reductive Nucleophilic Addition to Tertiary Amides. Chem. Lett. 2019, 48, 1138–1141.
47. Yoritate, M.; Takahashi, Y.; Tajima, H.; Ogihara, C.; Yokoyama, T.; Soda, Y.; Oishi, T.; Sato, T.; Chida, N. Unified Total Synthesis of Stemoamide-Type Alkaloids by Chemoselective Assembly of Five-Membered Building Blocks. J. Am. Chem. Soc. 2017, 139, 18386–18391.
48. Williams, D. R.; Shamim, K.; Reddy, J. P.; Amato, G. S.; Shaw, S. M. Total Synthesis of (-)- Stemonine. Org. Lett. 2003, 5, 3361–3364.
49. Shirokane, K.; Wada, T.; Yoritate, M.; Minamikawa, R.; Takayama, N.; Sato, T.; Chida, N. Total Synthesis of (±)-Gephyrotoxin by Amide-Selective Reductive Nucleophilic Addition. Angew. Chem. Int. Ed. 2014, 53, 512–516.
50. Blackburn, S. N.; Haszeldine, R. N.; Parish, R. V; Setchfield, J. H. Homogeneous Catalysis by Iridium (I) Complexes of the Reaction Between Silanes and Alcohols or Dideuterium. Journal of Organometallic Chemistry. 1980, 192, 329–338.
51. Key features of N-alkoxyamide derivatives. (a) Yanagita, Y.; Nakamura, H.; Shirokane, K.; Kurosaki, Y.; Sato, T.; Chida, N. Direct Nucleophilic Addition to N‐Alkoxyamides. Chem. Eur. J. 2013, 19, 678–684. (b) Barrios, F. J.; Zhang, X.; Colby, D. A. Dialkylaluminum N,O-Dimethylhydroxylamine Complex as a Reagent to Mask Reactive Carbonyl Groups in Situ from Nucleophiles. Org. Lett. 2010, 12, 5588–5591. (c) Kurosaki, Y.; Shirokane, K.; Oishi, T.; Sato, T.; Chida, N. Concise Synthesis of α-Trisubstituted Amines from Ketones Using N-Methoxyamines. Org. Lett. 2012, 14, 2098–2101. (d) Chiara, J. L.; Destabel, C.; Gallego, P.; Marco-Contelles, J. Cleavage of N−O Bonds Promoted by Samarium Diiodide: Reduction of Free or N-Acylated O-Alkylhydroxylamines. J. Org. Chem. 1996, 61, 359–360. (e) Ritter, A. R.; Miller, M. J. Amino Acid-Derived Chiral Acyl Nitroso Compounds: Diastereoselectivity in Intermolecular Hetero Diels-Alder Reactions. J. Org. Chem. 1994, 59, 4602–4611. (f) Gong, J.; Lin, G.; Sun, W.; Li, C. - C.; Yang, Z. Total Synthesis of (±) Maoecrystal V. J. Am. Chem. Soc. 2010, 132, 16745–16746. (g) Yoritate M. Two-step Synthesis of Multi-substituted Amines and Unified Total Synthesis of Stemoamide-type Alkaloids. Ph.D. T. Keio University, Japan, 2017.
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53. Selected example of reports on proximity effect of two Si–H groups. (a) Nagashima, H. Efficient Transition Metal-Catalyzed Reactions of Carboxylic Acid Derivatives with Hydrosilanes and Hydrosiloxanes, Afforded by Catalyst Design and the Proximity Effect of Two Si-H Groups. Synlett 2015, 26, 866–890. (b) Nakatani, N.; Hasegawa, J. Y.; Sunada, Y.; Nagashima, H. Platinum-Catalyzed Reduction of Amides with Hydrosilanes Bearing Dual Si-H Groups: A Theoretical Study of the Reaction Mechanism. Dalt. Trans. 2015, 44, 19344–19356.
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55. Examples of nucleophilic addition to amides utilizing N-acyliminiumion. (a) Suh, Y. G.; Shin, D. Y.; Jung, J. K.; Kim, S. H. The Versatile Conversion of Acyclic Amides to α-Alkylated Amines. Chem. Commun. 2002, 2, 1064–1065. (b) Suh, Y. G.; Kim, S. H.; Jung, J. K.; Shin, D. Y. The Versatile Conversion of Lactams to the α- Alkylated Azacycles via Cyclic N,O-Acetal TMS Ether. Tetrahedron Lett. 2002, 43, 3165–3167. (c) Jung, J. W.; Shin, D. Y.; Seo, S. Y.; Kim, S. H.; Paek, S. M.; Jung, J. K.; Suh, Y. G. A New Entry to Functionalized Cycloalkylamines: Diastereoselective Intramolecular Amidoalkylation of N,O-Acetal TMS Ether Possessing Allylsilane. Tetrahedron Lett. 2005, 46, 573–575.
56. Huang, P. Q.; Huang, Y. H.; Xiao, K. J.; Wang, Y.; Xia, X. E. A General Method for the One-Pot Reductive Functionalization of Secondary Amides. J. Org. Chem. 2015, 80, 2861–2868.
57. Cheng, C.; Brookhart, M. Iridium-Catalyzed Reduction of Secondary Amides to Secondary Amines and Imines by Diethylsilane. J. Am. Chem. Soc. 2012, 134, 11304–11307.
58. Yao, W.; Fang, H.; He, Q.; Peng, D.; Liu, G.; Huang, Z. A BEt3 -Base Catalyst for Amide Reduction with Silane. J. Org. Chem. 2019, 84, 6084–6093.
59. During the preparation of this dissertation, the group of Huang independently reported the elegant reductive nucleophilic addition to secondary amides using the Brookhart’s catalytic system, see: Ou, W.; Han, F.; Hu, X. N.; Chen, H.; Huang, P. Q. Iridium-Catalyzed Reductive Alkylations of Secondary Amides. Angew. Chem. Int. Ed. 2018, 57, 11354–11358.
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