Pd錯体を用いた触媒反応及び有機触媒を用いたリビングラジカル重合反応の反応機構に関する理論的研究

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(1)Pd (Theoretical study on the mechanism for catalytic reactions using Pd complexes and living radical polymerization using organic catalysts). 28. 9.

(2) 28. 9.

(3) 1 3 N-N. (II). Heck. 1.. 5. 2.. 12. 3.. 16 3-1. 3-2. Pd(II) 3-3. Pd(II) 3-4. 3-5. P-P. N-N. 4.. 43. 5.. 44 Pd. 1.. 47. 2.. 50. 3.. 54 3-1. 3-2. 3-3. 3-4.. 4.. 73. 5.. 74. 1.. 77. 2.. 84. 3.. 88.

(4) 3-1. Activation 3-2. 3-3. Deactivation 4.. 103. 5.. 104 106 108.

(5) 1 2. 2. [1]- [12]. A+B. C 1. A+B. 2. 2. 1 2. (. ) 2. 1. 1. 2.

(6) (. (. ). ). Figure 1. 9 A9. Figure 1. A1.

(7) (TS). TS. [1] P. Ruiz-Castillo, D. G. Blackmond, S. L. Buchwald, J. Am. Chem. Soc. 137 (2015) 3085. [2] G. C. Fu, J. Org. Chem, 69 (2004) 3245. [3] T. Fujihara, K. Semba, J. Terao, Y. Tsuji, Angrew. Chem. Int. Ed. 49 (2010) 1472. [4] K. Selevakumar, A. Zapf, M. Beller. Org. Lett. 4 (2002). [5] J.M. Caruthers , J.A. Lauterbach, K.T. Thomson, V. Venkatasubramanian, C. M. Snively, A. Bhan, S. Katare, G. Oskarsdottir, J. Catal. 216 (2003) 98. [6] C. Wang, T. Hisatomi, T. Minegishi, Q. Wang, M. Zhong, M. Katayama, J. Kubota, K. Domen, J. Phys. Chem. C, in press. [7] T. Mitsudome, T. Urayama, K. Yamazaki, Y. Maehara, J. Yamasaki, K. Gohara, Z. Maeno, T. Mizugaki, K. Jitsukawa, K. Kaneda, ACS Catal. 6 (2016) 666. [8] O. Niyomura, M. Tokunaga, Y. Obora, T. Iwasawa, Y. Tsuji, Angrew. Chem. Int. Ed. 42 (2003) 1287. [9] J. G. Seitzberg, C. Dissing, I. Søtofte, P. O. Norrby, M. Johannsen, J. Org. Chem. 70 (2005) 8332. [10] Y. Ma, P. B. Balbuena, Chem. Phys. Let. 440 (2007) 130. [11] Y. Zhu, D. G. Drueckhammer, J. Org. Chem. 70 (2005) 7755. [12] M. Matsugi, Y. Kobayashi, N. Suzumura, Y. Tsuchiya, T. Shioiri, J. Org. Chem. 75 (2010) 7905..

(8) N-N. (II) Heck. S. Sanada, T. Kuroda, M. Sumimoto, K. Hori, J. Comut. Aided Chem. 16 (2015) 30..

(9) 1. Heck [1]. Heck. 1971 [2]-[13]. R1-X. Pd(0) or Pd(II). R2. +. R2. 1. R. (X=halide,OTf). Pd0/PdII. Heck. [14]-[21]. Scheme 1 R1-X. Pd Pd-R1. R1-X. PdL2. H-X. oxidative addition. reductive elimination H X. R1. Pd. L. X. L. L elimination. R. 1. Pd. R1. R2 X. olefin insertion R2. Pd. L. L Scheme 1. Pd(0). Heck. R2. L.

(10) 0 B J. Shaw [22]. PdL2Cl2. 2. Pd((PPh2)2CH2Cl2). Pd(II). Heck Herrmann. Pd0/PdII. PdII/PdIV Scheme 2. Pd(II). [23]. X-. PdL2X2. Pd(0). L L Pd X. -X. X. L L PdII. H-X. oxidative addition. reductive elimination X L L. R. 1. R1-X. X. PdII. X R1 L PdII L X. H. X. R2. olefin insertion. elimination X L IV R2 Pd L X R1. Scheme 2 Pd(II). R2. Heck.

(11) Pd. Heck. Suzuki Coupling. Stille Cross Coupling Pd [24]-[25]. M. Emre. Figure 1. Heck. Heck. [26]. R R. entry. Pd catalyst. Yield(%). 1. A. 77. 2. B. 79. 3. C. 66. 4. D. 52. 5. E. 50. 6. F. 53. Figure 1. M. Emre.

(12) H. J. Fu. Figure 2. Heck (Figure 2) [27]. 1,4-dioxane. TBAE (Entry 10). Entry 10. Figure 2. Dave-Phos.

(13) Sumimoto. P-P. [28]. Pd II. Heck. IV. Pd /Pd. Pd0/PdII (Scheme 3) LL. Pd. 6. L. L L Pd Br. C2H4 L. L. Oxidative Addition. L Pd. Erhylene Coordination. L Pd. Br. Br H-Br. Erhylene Insertion. Reductive Elimination. L L Br L Pd Br. L Pd Br. H. b-H Abstraction. C6H5Br Coordination. L Br. L. L Pd Br H. L Pd Br H. Scheme 3. Sumimoto. Pd(II). Heck.

(14) Mizoroki-Heck. Pd P. L. N. Pd. P Pd P. N [29]- [33]. Pd Hayashi. 2-(2'-. ). Scheme 4. [34]. N,N-. Y. Y=S. Y=O. YH. + CHO. NH2. Y = NH. O2 100 w % Shirasagi KL. Y. N. xylene, 120 C°. N. 2-(2-. ). N. (Y = NH, O, S). Scheme. Pd(II). Mizoroki-Heck. S. Haneda. 2-(2-. ) [35]. -. (Scheme 5) Y NH O S. 97. Scheme 5. 83 75%. 1(Reaction a : 1a Reaction b : 1b Reaction c : 1c) Heck 1 Pd(II). Heck.

(15) Scheme 5 Haneda S. Haneda. Heck (DFT). [36].

(16) 2. [37]. Gaussian09 -tert-. (DFT). B3PW91. Hay-Wadt. ECP. (541/541/211/1) [38]-[40]. C Br Cl. Pd. split valence 6-311G(d) H. 6-311G(d,p) N. 6-311G(2d) B3PW91 Pd. 6-31g(d). (Scheme 6) N. N. N Ph. Pd. Pd Ph. Br. N. Br. Scheme 6 1. 2. 1. Gaussan09 (Figure 3). Figure 3. DFT.

(17) 3. 2 4. 3. TS(. ). TS. (Figure 4). Figure 4 TS 5. 4. TS (Figure 5). Figure 5.

(18) 6.. TS. IRC(. ) 7.. SMD DMF(N,N-. [41]. SMD. ) TS. Ea. E. G. Whiteside[42]. Figure 6. A. A. A. A. Figure 6 Figure 6 Figure6. 2 2. A A. (2.1). (. (2.2) (2,3). ) (2.1).

(19) H. T. G= H- TS. (2.4). H=Ea-RT. (2.5). (2.5). (2.5). RT. (2.2) (2.3) (2.6). (2.6). gass phase. Ea. E G. G. S. (2.4).

(20) 3. 3-1. Heck. 2c. (Scheme 7). 2c. Cl-. c 2c. N1. N Cl. PdII N2. -. -Cl. Cl. PdII N2 Cl. 1. Scheme 7. 2. Cl-. Figure 7. 1c. 2c. Figure 7. 1c 2c. Heck. Scheme 8. 2c. 2c 3c Br-Ph. Ph-Br. C 2H 4 Pd-N1 IV. Pd. 3c 4c. 5c.

(21) N1. N1. Ph Br. Ph. Br. Br. 1. N. PdII N2. PdII N2. Cl. Pd. Cl. Cl. 2. II. 3. N. Ph. 5. 3c (3c. 4 c) Ph-Br. (4 c. 5 c). 17.1 54.0 kcal/mol 3c. Cl. Ph-Br. 2c Ph-Br. PdIV N2. 2. 4. Scheme 8 2. N1. Figure 8. Pd-N(1). 2.092 Å. Å. TS3c-4c TS4c-5c, 5c. TS3c-4c, 4c Pd-N(1). Pd-N(1). 2.510, 2.258. 4c 2.728, 2.273 Å. Pd-N(1). Figure 8 Ph-Br. Scheme 9 5c 7c. Pd-C. 6c.

(22) Br. Br. N1. PdIV N2 Ph. Br. N1. Ph. PdIV N2 Ph. Cl. PdIV N2 H. Cl. 5. N1. 6. Cl 7. Scheme 9 5 5c. 6c. TS. TS5c-6c Ea. 6c (6c. 7c) Ea 6c. 5c. 5c. 20.0 kcal/mol. 13.4kcal/mol. 2.238, 2.367 Å C(2)-C(3). 0.1 kcal/mol. Pd 2.279, 1.545 Å. Pd-C Pd-N(1), N(2). 2.062, 2267 Å. TS6c-7c. 2.265 Å Å. 6c. Figure 9. TS5c-6c, 6c 6c. 7c. 7c. Pd-N(1), N(2) 6c. 0.6 kcal/mol. 7c Pd-N(1). Figure 9. Pd-N(2). 2.005, 2.093, 2.190.

(23) 7c. Scheme 10. 7c. 8c. 10c. H-Br. Br Ph. Br. N1. Ph. PdIV N2 H. 10c. PdIV N2. Cl. H Cl. 7. 8. 10c. H. N1. -. Ph. Br. N1. N1. HBr. PdII N2. PdII N2. Ph. Cl. Cl 1. 9. 0. Scheme 10 7 Ea 10c 7c. 3c. Pd-N(1). 3.4 kcal/mol 1.697 Å. 8c. TS7c-8c, 8c. Pd-H. (1). 2.248 Å 8c, TS8c-9c, 9c. 2.248, 2.378, 2.569 Å. 1.578, 1.503 Å 2.093, 2.159,. Pd-N(1). TS9c-10c, 10c Pd-N(1). Figure 10. Pd-N(1) 2.436, 2.096 Å.

(24) Figure 10. (7c. 8c. 9c. 10c).

(25) 2c. Heck. Table 1 Figure 11. Table 1. 2c. (Ea. Path. Ea. 3c. 4c. 17.1. 13.9. 4c. 5c. 54.0. 36.1. 5c. 6c. 36.7. 16.1. 6c. 7c. 29.5. 16.0. 7c. 8c. 16.7. 14.2. 8c. 9c. 19.5. 6.2. 9c. 10c. 9.2. -3.4. 3c 4c. : kcal/mol. 5c. 54.0 kcal/mol. 3c. 10c. kcal/mol 2c. 1c. Cl-. 3c. Cl-. 2c. 1c Pd-Cl. 133.6kcal/mol 2c. 10c. 3.4.

(26) Figure 11. 3c. Heck.

(27) 3-2. Pd(II) 3-1. Cl-. 1. 1c. C2-H4 Ph-Br 1c. Ph-Br. 1c C-Cl. Ph-Br. 13c. Scheme 11. 1 Scheme 11 13c C-Cl. Ea. 68.1 kcal/mol. Ea. E 13c 1c. 39.4kca/mol.

(28) 3-3. Pd(II) 1c. C2-H4 1c. (Scheme 12). Pd. 14. Pd-Cl. 15c Figure 12. N Cl. N1. C 2H 4. Pd. PdII N2. Cl. Cl. II. N. N1. 2. Cl. Cl. 1. PdII N2. Cl. 14. 15. Scheme 12 1 1c. Pd-C(1), Pd-C(2). 4.923, 4.279 Å. TS1c-14c, 14c. 2.495, 2.444 Å. 14c. Å. 15c. (1). 2.709 Å. 14c. 14c, TS14c-15c, 15c. 2.186, 2.119, 2.026 Å 15c C(2)-Cl 15c Pd-C. 4.923, 4.279. 1.825 Å. 2.093, 2.305, Pd-N(1) Pd-C(1).

(29) Figure 12. 1c. 15c. Scheme 13. Scheme 13 15. C-Cl. 15. 2. 2 Pd(0). 16 17. Figure 13.

(30) 15c, TS15c-16c, 16c. 1). 2.210, 2.645, 2.773 Å 0.563 Å. Ea. E. Ea. 2. E. 17 15 17. 15c. Pd-N(1). 57.2, 43.5 kcal/mol. 15. Figure 13. 16c. 16c 17c. 25.8, -5.3 kcal/mol Ea. 17. 31.4 kcal/mol.

(31) 17. Scheme 14. Br. N1. PdIV N2. Cl Ph. Cl. Scheme 14 17. -ClC2H4Cl. N1 PdII N2. Br Ph. 17. 13. ClC2H4Cl. 13. 17 Figure 14 17c, TS17c-13c, 13c. Cl. 2.375, 2.423, 5.077 Å. 5.137 Å. 13c C-Cl. 0.563 Å. 2.065, 2.495, Cl,. C. 3.241, 2.338, 1.807 Å 16c. Pd-N(1). 17c E. C. 34.5, -49.6 kcal/mol. Figure 14. 13c. Ea.

(32) 1. Ph-Br. 13c Scheme 15. Scheme 15 13 1 14 15 17 13 Sumimoto G 15. G. Figure.

(33) Figure 15.

(34) 3-4. Pd(II). 13 Sumimoto =. N1 Br Pd N2. N1 Ph. Ph. N1. N2. Pd. Pd Ph. N1. N2. Br. Br. Br. Pd H. Ph. 13. 18. 19. Scheme 16 13 a b c. 13. 3. 20. 20. 20. Figure 16 17 18 Table 2. 20. 3. (Scheme 16). 13. N1 Pd. 18 Pd-C. 18 Pd-N1. 19. 20. Table 2 13. 20. G. Path 13-18. G. Path 18-19 G. Path 19-20 G. G. 14.0. -7.6. 7.3. -14.7. 5.5. 15.9. -5.1. 4.7. -15.1. 6.3. 15.7. -5.5. 4.5. -15.0. Y. G. a. 16.9. 9.4. b. 14.5. c. 15.1. G. : DMF. G. : kcal/mol. N2.

(35) Figure 16. 20c.

(36) Figure 17. 20b.

(37) Figure 18. 20a.

(38) N1. Pd. 4. 18a 19a. 18 19. TS18a-19a. TS19a-20a. TS18-19. TS19-20. Figure 18. 180°. Br-H. 2.362 2.363Å. Br-Hr. b c. G. 2.425 2.328. Path 18-19. G. G. a Br-H. 18a. 1.9 1.7kcal/mol TS18a-19a. G. a. G. G. 2.5 2.1kcal/mol. 19a 0.083 0.097Å. Br-H. G. 20. Scheme 17. a,b,c. G. 20. 23. Figure 19 20 21 Table 3 N1 Pd. Br. N2. Br N1 Pd. H. N. H. Pd. H Ph. Ph. 20. 21. 22. Scheme 17 20 20. Ph. Br N1. 2. 21. 23 22. 23. 2. N1. N. H Pd N2. Ph. Br. 23.

(39) Figure 19. 23c.

(40) Figure 20. 23b.

(41) Figure 21. 23a.

(42) Table 3 20. 23. G. Path 20-21. G. Path 21-22. Path 22-23. Y. G. G. G. G. G. G. a. -. 15.5. -. -3.0. 7.3. -6.4. b. -. 15.1. -. -2.5. 6.7. -5.3. c. -. 13.8. -. -2.4. 6.9. -5.8. DMF Path 20-21. a b c. a b c. : kcal/mol. 21 20. 22 21. Path 22-23. 6.7 6.9kcal/mol. G. Path 20-23. G. 23. Path 21-22. a b. G. c. a b c. 7.3. -6.4 -5.3 -5.8kcal/mol. G. Scheme 18. 23. 13. Figure 22. N1 H Pd N2. Ph. Ph-Br H. Br. Br N1 Pd. H-Br N2. N2. N2. N1 Pd. N1 Pd. Br. Br 24. 23. 25. Scheme 18 23 23. Pd. Ph. Pd-Ph 13 (Figure 22). Pd. N2. Ph. 13. 13 24. 25 26. Ph. Br. 26. C6H5Br Pd(0). Br. N1. 25 Ph-Br. HBr. Pd-Br TS26-13.

(43) Figure 22 24. 23. 13. c. Scheme 19. 24 TS24-27. Br. 28. G. G. Br HBr. G. 13. Ph-Br. 5.0 kcal/mol 28. (27 G. 18.8 kcal/mol. ( 27. 28 ). 13). 20.1 kcal/mol. 7.9, 5.7 kcal/mol. Pd. HBr a. G. 27. Ph-Br. b. G c. G. b, c. 6.6 kcal/mol. Br. 1.3, 2.1 kcal/mol. 13. a. HBr 2.0, 2.4 kcal/mol. G. (24. 27 ). (27. 28 ) 19.1,. 20.1 kcal/mol. Ph H. Br N1. Br N1 Pd Br 24. N2. H Ph. Pd. Br N1 2. Pd. N. Br. Ph. Br. H-Br 2. N. N1 Br Pd N2 Ph. H 27. Scheme 19 Ph-Br. 28. 13.

(44) 13 Y=NH TS. Figure 23 13. Figure 23. 13. Y=NH. Ph-Br. 2. Scheme 18, 19. HBr. 13 13. 18. 19. 20. 21. 22. 23. 24. 13. 25. 26 (18. 19 ) Scheme 20 PdII/PdIV. N-N. Pd0/PdII. P-P N-N, P-P 13c Br-H. Pd-N(1). Pd0/PdII 180°.

(45) N1 Br N2 N1 Pd Br. Ph. Pd. C2H4 2. N. N1. Ph Oxidative Addition. N2. Ethylene Coordination. Pd. Ph. Br Ethylene Insertion. N2. N1. N1 Pd. Ph H. Ph. Ph. Br HBr. N2. Pd Br. H-Br Elimination Br N1 Pd. N1 Pd. Br. N2. H. Br Ph b-H Abstraction. Ph-Br Coordination N1. Ph-Br. H Pd N2. Br N1. Styrene Elimination. Pd. Br. H. Br N1 Ph. H. Pd. N2 Ph. Scheme 20.. Ph. N2. N2.

(46) 3-5. P-P. N-N N-N. Heck. Pd. 4. 6. Sumimoto Pd. N-N. Pd-N. P-P P-P Figure 24. Pd-N(1) Pd-P(1). Pd-N(2) Pd-P(2). Pd N-N, P-P 22.6kcal/mol 6. P-P Heck. N-N. Figure 24 P-P N-N. Pd.

(47) 4. DFT. Mizorokie-Heck.

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(50) Pd. S. Sanada, M. Sumimoto, K. Hori, Int. J. Org. Chem. 5 (2015) 246..

(51) Pd [1]-[5] [6]-[10]. [11]-[15]. [16]-[20]. Cr [21]-[22]. Scheme 1. Scheme 1. Cr Pd Scheme 2. Pd. [23]. Pd. Si-Si. CNSiMe3 Scheme 3. [24]. Pd. R. Si Si. R = Ac, COCF3. Scheme 2. CN-Si. Pd cat. R. Si.

(52) R. Pd cat. CN Si. OY. R. CN. R = Ac, CO2Me Scheme 3. [25] [26]. Scheme 4. R3. O R. 1. R. A. R2. 1. R5 R4. R3. [Pd]. OCORB. R. 2. Reaction. RA. RB. SnMe3. CF3. SiMe3. CF3. SiMe3. CH3. R5. 2. R1. RBCOORA. R4 O 3. 4. Scheme 4 THF( 3. (Reaction I :. II-2. (RB=CF3. Reaction I. Reaction III :. ). Pd I-2 (RB=CF3. I-1. III-1 III-2. Reaction II. Reaction II :. (RB=CH. 3. Reaction I Reaction II Reaction III. II-1 3 Reaction I.

(53) Scheme 5 PdL 2. -. 1. -. -. R1. 4 3. PdL. OCORB 2. PdL. O 3. L. Pd. R. 1. RA : SiMe3, SnMe3 RB : CH3, CF3. Pd L O R. O. O RBCOORA 4 Scheme 5. R1. RA 1. B. O.

(54) 2. 09 (TS). (DFT). B3PW91[29]-[30]. Pd. split valence H. Hay-Wadt. (541/541/211/1). 6-31G(d,p) Si. ECP C O. 6-311G(2d) Sn. Lanl2dz. Scheme 6. (1) C. C(1) Pd R. B. O (2)C O O(1) RA. RB. O O. Pd. C(2) O. RA. Scheme 6 8. 9. 1. Gaussan09 (Figure 1). Figure 1. DFT. 6-311G(d).

(55) 10. 2. 11. 3. TS. TS. (Figure 2). Figure 2 TS 12. 4. TS (Figure 3). Figure 3.

(56) 13.. TS. IRC(. ) SMD[34]. 14.. SMD. THF. [35]. A. A. A. A.

(57)

(58) 3. 3-1. Scheme 7 Pd. Pd. 6. 5. 5. 1. 2. 6. 7. 7 O. [Pd]. OCORB. Pd O O. RB. O O Pd. 2. RB. Pd O O. Pd O O. RB. RB. 6. 6. 5. RA 1 RB. O. Pd O. O. RA 7. 7 7. R. B. Scheme 8 7. C(1) Pd O O C(2) O(1) RA. RB. 7 R : SiMe3, SnMe3 RB : CH3, CF3 Scheme 8 7 O(1) Sn Si TS8-9. RB. 8. O RA. 7 TS8-9. Sn Si-C(2) 8. C (1)-C(2). 9 Figure 5 6 7. O. C(1) C(2) Pd O. 9. 8. A. Sn Si-O(1). C(1) Pd O (2)C O O(1) RA. 7 8 9 Table1.

(59) I-7 I-8. Sn-C. I-7. 2.238 Å I-TS7-8 2.585Å I-8 4.900Å. Sn-C. Sn-O(1). I-7 2.749 Å I-TS7-8 2.286Å I-8 2.073Å I-8. I-7. Sn-O(1). Sn-O(1). Pd-C(2). I-8. I-9. I-8 2.014 Å I-TS8-9 2.075Å I-9 3.963Å. Pd-C(2). I-8. I-9. -. 7. 8. 9. II. III 7 8. I II III. I II. 27.1 39.1 30.1kcal/mol I. 8. 8 9. 12.0kcal/mol I II III 9 8. 20.0kca/mol. I-7 Sn-C II-8. I Si-O(1). Si-O(1). II-7. II. II-7. 3.030 1.740Å Si-C. 7. 12.7 12.6 3.9kcal/mol. I II II-8. 8. I II. 0.281 Å. I-8 Sn-O(1). 0.333 Å Si-C Si-O(1). Sn-C Sn-O(1). Sn I. II. Table 1 7. 9 Path 7-8. Path 8-9 G. G. I. 27.1. -8.5. 12.7. -21.2. II. 39.1. -7.8. 12..6. -21.7. III. 30.1. -19.2. 3.9. -34.8 : kcal mol-1. Si.

(60) Figure 5. I-9.

(61) Figure 6. II-9.

(62) Figure 7. III-9.

(63) 9. 9. Pd(0). 3 4 III. III. I II. III. Figure 8 Pd(0)+3+4 9. Figure 8. 9. 29.2kcal/mol. Pd(0). 3 4. 9. Scheme 9. 9. 2. 10. I II III. Figure 9 10 11 RB O. Pd R. B. O. C(1) C(2) O. O Si Me Me Me. O OCORB Pd. 2 RB. O. O O Si Me Me Me. 9. Scheme 9 9 2. 10. 10.

(64) Figure 9. I-10. Figure 10. II-10.

(65) Figure 11 III-10 I. I-9 Pd-C(1) Pd-C(2). 3.333 3.888Å Pd-C(1) Pd-C(2). 4.392 4.512Å Pd-C(1) Pd-C(2). 2.123 2.162Å I-10 I-9 II II-10. Pd-C(2) III. 8.3kcal/mol II-9 Pd-C(1) Pd-C(2). Pd-C(1) Pd-C(2) II-10. I-10. Pd-C(1) Pd-C(2). 2.0kcal/mol 4.489Å. I-TS9-10. 2.123 2.162Å. Pd-C(1). II-9. 3.2kcal/mol. III-10 Pd-C(1) Pd-C(2). G 10. 9 10. 4.363. 9. 1.2kcal/mol.

(66) 10. 10 10. Pd-O. 5. Pd 4. 4. 11. I II III. 11. Figure 12 13 I-11 II-11 III-11. Pd-O(2). 6.885 9.672 6.428Å. 4. Pd-O(2). I-11 II-11 III-11. 2.396 2.357Å. Pd-O(1). I-11 II-11 III-11. I-10 II-10 III-10. Figure 12. 5 13.8 11.8 7.7kcal/mol. 11. Figure 13. I-11 II-11 III-11. Pd-O(1) 11. 2.375.

(67) 11. 11. B. 10 11. R COOR. 12. A. I-11 II-11. 11 12. I II. I. I III. 12. Figure14 15 I. I-11 I-TS11-12 I-12 Pd-C(3) Pd-C(3). I-TS11-12 I-12 C(3)-O. 0.835 Å. I-11. 1.466 1.941 2.920Å TS -. 10.4kcal/mol. C(3)-O. C(3)-O 12. I-12 I-11. I-11 I-12. III-11 III-12. III-11 III-TS11-12 III-12 Pd-C(3). 2.987 2.770 2.126Å. Figure 14. II-11 III-TS11-12. 1.453 2.030 3.441Å 16.5kcal/mol. I-12 II-12. G. 10.5kacal/mol. Pd-C(3) III-12 C(3)-O. 1.454Å. C(3)-O. Pd-C(3). III. 3.012 2.848 2.177Å. C(3)-O III-12. III-11. 3.4kacal/mol.

(68) Figure 15 12. III-12 12. 3. 6. I III. 12. Figure 16 17 I. I-12 I-TS12-6 I-6 Pd-C(1). 3.196 4.734 Å. 2.288 2.912 5.343Å Pd-C(2). I-6 Pd-C(1) Pd-C(2) I-12 I-TS11-6 I-6 Pd-O(1). 3. 3.226 2.171. I-6 Pd-O(1) III. 2.292. 2.216Å. 10.5kcal/mol III-12 III-TS12-6 III-6 Pd-C(1). 2.260 3.027 5.871 Å 2.758 2.144. III-11 III-TS11-12 III-12 C(3)-O. 2.161Å. III. 9.1kcal/mol I-III. I 6. 6 1. 2.260 2.810 6.763Å Pd-C(2) C(3)-O. 1.9kcal/mol 3. 7.

(69) Figure 16. Figure 17. I-6 II-6. III-6.

(70) 7 7 Scheme 10. Figure17. I II III. Figure 18 19 20 7 8 III. I II. 27.1 39.1 30.1kcal/mol. I. II RA. SnMe3. 13.0kcal/mol. SiMe3. II. I III. II. 9.0kcal/mol. O A. 1. R. RB. Pd O O. C(1) Pd O O C(2) O(1) RA. C(1) Pd. 7. RB. RB O. 6. O (2)C O O(1) RA 8. 3 (1) C O B. R. Pd O 12. Pd RB. O. O. O. RB O Pd. O. Scheme 10. O. RB RBCOORA. 11. RB. 4. O O. C(2) O. 9 RA OCORB. O. Pd O. O. A. R. 10. 2.

(71) Figure 18. I.

(72) Figure 19. II.

(73) Figure 20. III.

(74) 3-2. I. II RA II. 13.0kcal/mol. SiMe3. SnMe3. I .. 7 8. C-SiMe3 C-SiMe3. C-SiMe3. Figure 21. C-SnMe3. C-SnMe3. C-SnMe3. C-SnMe3. C-SiMe3. SnMe3. Figure 21. 19.0kca/mol 7 8. RA. SiMe3.

(75) 3-3. 7 8. III. II. 9.0kacal. III 6 7 6. 1. 7. 7. Figure 22 I-7. I-6+1. 2.5kcal/mol. II-7 III-7. I-7 III RB. Figure 22. II-7. III-6+1. 6+1. 7. 25.2kcal/mol III-7. III-7 (CF3). II-6+1. (CH3). 1.6kcal/mol.

(76) 3-4. (6. 7). 7. (7. ). G Si ( Reaction IV : (RA=PbMe3, RB=CF3) ) 7. 8). G 7. Pb Me3 Reaction I IV. G 6. Sn. Figure 23. Reaction IV RB. 2.0kcal/mol. PbMe3 RB. 26.1kcal/mol. Figure 23. (6. SnMe3. 1.0kcal/mol. G. G (6. 7). 7 G.

(77) 4. Pd. 1. 2. 7 (1)Sn Si (2)8. 7. O(1). C(1)-C(2). (3). 2. (4) 10. 9. TS7-8. 8. TS8-9. 9. 10. Pd-O(2). 4. (5) 11. -. (6) 12. 5. 12. Pd-C(1) Pd-C(2). (7). 6. 3. 1. 6. 7. I. II. III RA. I II C- R. 11. SiMe3. C-SnMe3. A. C-SiMe3. C-SiMe3. 7 8 C-SnMe3. C-SnMe3. C-SnMe3. 19.0kca/mol. C-SiMe3. 7 8. RA. SiMe3. SnMe3 I II III. III 6. I-7 II-7 I-6+1. I-6+1 II-7+1. 1. 7. 2.5 1.6kca/mol. III-7. 5.2kcal/mol III. I II. I-7. 7 RB. 7 (CF3) (6. (CH3) 7) (7. 7 8). G.

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(80) A. Goto, S. Sanada, L. Lei, K. Hori, Macromolecules. 49 (2016) 2511..

(81) Scheme 1. AIBN. C2H2. (1) AIBN C 2H 2 (2) C2H2 (3). (4). Scheme 1.

(82) (PDI) (Mn). (Mw). PDI. Mw/Mn. 1 (. ) PDI 2 2 2. PDI 3. PDI 2 3 (ATRP). (RTCP). (RCMP). ATRP. C-C. ATRP (Scheme 2). (1)Cu(I) Polymer. Polymer-X M. P. (3). X -Cu(II). Polymer-M. (2). X2-Cu(II). X. Scheme 2. C. R. Becer. 4. (MMA) ATRP. (Figure 1) [MMA] / [EBiB] / [Cu(I)] / [Cu(II)] / [HOEGTETA] [MMA] / [EBiB] / [Cu(I)] / [Cu(II)] / [HOEGTETA] / [PEG300]. 200 : 1 : - : 1 : 1. 200 : 1 : - : 1 : 1: 1. Cu(I) Cu(I) Cu(II). MMA.

(83) Figure 1. MMA. ATRP. ATRP ATRP Figure 2. ATRP. Figure 2. ATRP.

(84) (RTCP). Goto. Polymer-X(X. ). [25]. N-. (NIS). 2-. (AIBN) (MMA). Scheme 3. NIS NS. NS. Polymer. NIS. AIBN Polymer-I. MMA. Polymer-MMA. Polymer-MMA-I 1.38 MMA. (GMA). (BzMA). (MAA). Scheme 3 Goto. Goto. LRP. 2011. (ATRP). ATRP (Scheme 4) [26]. (RCMP). (TBA) (TMG). (TIO). TBA TMG. TIO I2 (Figure 3). TBA PMMA-I. TBA (Figure 4). TBA PDI MMA. G. 25.1kcal/mol.

(85) Scheme 4 Goto. Figure 3. ln([M]0/[M]) vs t/h. LRP. Mn/1000, Mw/Mn. conversion.

(86) Figure 4 RCMP RCMP. (Table 1) RCMP. 70. RCMP Table 1 RCMP. ( 125 ). RCMP. ( 70 ).

(87) RCMP ATRP R M. I2. RM. R-I. R-I R-I RM. R R. R-M-I. (Scheme 5) [27]. Scheme 5 (RCMP) A TBA TIO. (TEA) Reaction I, II, III. A. TEA TMG.

(88) 2. [28]. Gaussian09 (TBA). (TEA) MP2. I. LANL2DZ. 6-31G(d) MP2. I. 6-311++G(2d). 6-311++G(d,p) (Scheme 6). P. I A. I2 A. I P. Scheme 6 15. 16. 1. Gaussan09. MP2. (Figure 5). Figure 5. 17. 2. (Minp). TS.

(89) 18. 3. TS(. ). TS. (Figure 6). Figure 6 TS 19. 4. TS (Figure 7). Figure 7 20.. TS. IRC(. ) 21.. SMD. [30]. SMD.

(90) MMA. ( 6.32). ( 6.2528). TS. Ea. E. G. Whiteside[31]. Figure 8. A. A. A. A. Figure 8 Figure 8 Figure 8. 2 2. A A. (2.1). (. (2.2) (2,3). ) (2.1).

(91) H. T. G= H- TS. (2.4). H=Ea-RT. (2.5). (2.5). (2.5). RT. (2.2) (2.3) (2.6). (2.6). S. (2.4).

(92) 3. 3-1. Activation Goto. Scheme 7. SET (single electron transfer ). ISET(inner sphere electron transfer ) 2. ISET SET. A. ATRP. P-I. P-I P. I-. I [32]. P. I-A. SET 2. Scheme 7 ISET A. SET. a(TEA) b(TMG) c(TIO). (1). TS. Figure 9 Reaction I, II, III G. G1. 39.7. 10 11 12 53.6 93.8kcal/mol. 34.8 58.3 43.9 kcal/mol. Reaction I II III Reaction I, II, III. 1. (1)Reaction I P-I. G1. 39.7kca/mol. A P + I-A. G. G1. P-I + A. b. c. 34.8kcal/mol Reaction II. III.

(93) Figure 9. TEA. 1+TEA. O-H(1) O-H(2) O-H(3). O-H(2). P-I + A TS1a P + I-A. 2.640 2.890 3.633Å TS1a. O-H(1) O-H(3). 1.900 Å. O-H(1). O-H(1). 4.790 Å. O-H(1). 2.588 2.426Å. TS1a. 1+TEA. O-H(2) O-H(3). O-H(2). 0.052 1.207 Å. O-H(3) P + I-A. O-H(1) O-H(2) O-H(3). TS1a. 5.326. O-H(1). 2.620 2.328Å O-H(2) O-H(3). 1+TEA. 0.020 1.305 Å TS P + I-A III. G1. Figure 9. O-H. Reaction II. G. A. TEA. P-I + A TS1a P + I-A. (2)Reaction II P-I. G1. 53.6kca/mol. P + I-A. 38.3kcal/mol. Reaction I. Reaction. III Figure 10. TMG. TEA. P-I + A TS1b P + I-A P-I + A. O-H(1) O-H(2). 2.291 2.819 Å. TS. O-H. O-H(1) O-H(2). 0.355 0.353 Å. (O-H(1) : 1.936 O-H(2) : 2.466 ) P + I-A. O-H(1) O-H(2). 2.153 2.133Å. TS1b. 0.138 0.686 Å A. TMG. TEA Reaction III. TS P + I-A G1. G. P-I + A.

(94) Figure 10. A. TMG. P-I + A TS1a P + I-A. (3) Reaction III P-I. G1. 93.8kca/mol. P + I-A. 43.9kcal/mol. Reaction I II TIO. P-I + A. O-H. TEA TMG. 2.415 Å TS1c. TS Reaction I. Figure 11 A. P-I + A. TIO. II. G1. P-I + A TS1a P + I-A. 1.

(95) Figure 12. P-I. SET. SET. TS Figure 13. C-I. 4.625 Å. Figure 13 ~ Activation ~ ISET. A. TEA TMG TIO. P-I + A. A. O-H. TS1. O-H. +A. O-H. A. O-H A. TS1. TEA TMG TIO TEA TMG. 1. TIO. O-H P-I + A. P + I-A. O-H O-H. 1. P-I.

(96) P-I G1. A. TEA TMG TIO. 39.7. 53.6 93.8kcal/mol SET. C-I. 4.625 C-I. P. I-. ISET. SET. SET. 3-2. P + I-A MMA(. ( Scheme 8 ). P. ). Scheme 8 Figure 14 TS2. 3.733 Å. 2.241Å. C(1)-C(2). C(2) P +M. Figure 14. C(1)-C(2). 1.492Å PM. 2.174 Å. P +M TS2. C(1)-C(2). C(1)-C(2). 1.599 Å.

(97) 3-3. Deactivation I-A. Deactivation Scheme 9 A. I-A. I-A. 2. I2-A2. TEA TMG TIO. Figure 15 16. 17. Scheme 9 A. I-A. I2-A2. TEA TMG TIO. 4. (1)Reaction I (7) I-A. G4 N-I. 8.0kca/mol 2.772Å. I-A. N-I. 0.054 Å TS3a. TS3a. 2 I-A. I2-A2. N(1)-I(1). 15.7kcal/mol 2.725 2.826 Å. 0.047 Å. I2-A2. I-A. I2-A2. I(1)-I(2) I2-A2. Figure 15. TS3a. I2-A2. Reaction I. 4.600 3.025Å 1.575Å. I2-A2. TS3a. I(1)-I(2).

(98) (2)Reaction II (7). G4. 15.7kca/mol. I2-A2. Reaction I. G4. 7.7kcal/mol. Reaction II I-A. N-I. 2.782Å. TS3b. N-I. 0.033 Å. I2-A2. TS3b. I2-A2. N(1)-I(1). 0.098 Å. 2.684 2.815 Å I2-A2. I-A. I2-A2. I(1)-I(2). 4.742 2.978Å. Reaction I. Figure 16. 22.5kcal/mol. Reaction I. I-A TS3b. 2 I-A. Reaction II. I2-A2. I2-A2. 1.764Å.

(99) (3)Reaction III (7). G4. I2-A2 I-A. 18.1kca/mol. 2 I-A. S-I. 26.0kcal/mol. 3.729Å. TS3c. I2-A2. TS3c. TEA. S(1)-I(1). I2-A2. I-A. I2-A2. I2-A2. I(1)-I(2). TS3c. 1.000Å I-A. S-I. 0.207Å. I-A. S(1)-I(1). Reaction I II. S(1)-I(1). Reaction I. 4.808 2.910Å. I(1)-I(2). Figure 17. TMG. 3.264 3.532Å. 0.465Å I-A. TS3a. Reaction I II. II. I2-A2. 1.898Å. Reaction I II. Reaction III I-A. I2-A2 I2-A2. Reaction I II III. I2-A2 I2-A2 I2-A. Scheme 10 A. I2-A2. I-N. I-S.

(100) Scheme 10 I2-A. A. I2-A. Figure 18 19. Reaction I II III A. TEA. A. 5.8 6.0 3.1kcal/mol. I2-A. (Figure 15) I2-A2. I2-A2. I(2)-N. 0.307Å. A. 2.519Å. TEA. 17). I2-A 0.338Å. TIO 0.128Å. I(2)-N A. 2.477Å. TMG. I2-A. I(2)-S. 3.404Å. A. TIO. I2-A. 0.300Å. A I2-A2. Figure 18. I2-A2. I2-A2. I(1)-I(2) I(1)-N(1) I(2)-N. I(1)-I(2) I2-A2. I(1)-S(1). (Figure. I(2)-S. TIO. TEA TMG 0.128Å. I(1)-I(2). Reaction I II III. I2-A2. I2-A. A I2-A. I(2)-N I2-A. TMG. I(1)-N(1). I2-A. I2-A A. I2-A2. I(1)-N(1). (Figure 16). I2-A + A. I2-A. N-I.

(101) Figure 19. I2-A. I2. I2-A. A. Scheme 11. Figure 20. Scheme 11 A. TEA. A. I2 + A. TMG A. TIO I2. A A. A. TEA TMG I-S. TEA. I-A A. I-S. TMG. I-N I2 + A. 8.0kcal/mol 4.5kcal/mol I2-A. 4.3kcal/mol. I-A. TIO. 0.885Å. A. I2-A. I2 + A. I2-A A. I2-A. I2 + A. I2-A. I2-A. I-N. 2.519 2.477Å. 3.404Å. A A. I-A. TIO. TIO. I-A 0.927Å A. I2-A. TIO.

(102) Figure 20 I-A. I2 + A (4)-(6). Figure 21. I2-A. I2-A. Figure 21. (4)-(6).

(103) I-A, I2-A2, I2-A, I2 I2-A2. I. A. I-A , I2-A, I2. Deactivation (Scheme 11) Figure 22 TS. (7)-(9) (8). Figure 23. (7). Deactivation. (A-I-I-A). I2-A2 P. P. 24 25. Reaction I, II, III. -43.9 kcal/mol. G. 4. 9, 15.3, 49.9kcal/mol. G. Reaction I, II. Reaction III. Scheme 11. Figure 22. I-A , I2-A, I2. I-A , I2-A, I2. Deactivation. Deactivation. -34.9, -38.3,.

(104) (8). I. G. (1)Reaction I (10). G5. 7.5kca/mol. P-I + I-A. Figure 23. P + I2-A. TEA. P + I2-A. O-H(1). P-I + I-A. O-H(1). P + I2-A. O-H(2). P + I2-A P-I + I-A. 2.298. O-H(2). 0.084Å. 14.7kcal/mol. 3.012Å. 2.382. 2.637Å. O-H(2). O-H(1). 0.375Å. TS. Figure 23. A. TEA. P + I2-A TS4a P-I + I-A. (2)Reaction II (10). G5. 12.5kca/mol. Figure 24. P-I + I-A. TMG. P + I2-A. 9.7kcal/mol. P + I2-A P-I + I-A. TEA P + I2-A P-I + I-A P + I2-A. O-H(1) O-H(1) 0.002Å. O-H(2). 2.075. O-H(2). 2.107Å. 2.073 O-H(2) A. TEA. 2.342Å 0.235. O-H(1) TS.

(105) Figure 24. A. TMG. P + I2-A. TS4a P-I + I-A. (3)Reaction III (10). G5. 3.6kca/mol. Figure 25. P-I + I-A. TIO. A. (9). TIO. P + I2-A TS4a P-I + I-A G. I2. Deactivation. -16.5kcal/mol. 18.2kcal/mol. P + I2-A TS5c P-I + I-A. O-H. Figure 25. P + I2-A.

(106) ~Deactivation~ I-A. Deactivation (Figure 21) I2-A2. I. I-A. I2-A I2 I2-A2. I2-A. A. (A-I-I-A). I2-A2. Deactivation. (Figure 22). 3-4. (1). TBA. TBA+I2 20%. Activation. Deactivation. Deactivation G. 4.9 7.5kcalmol. Deactivation I-A. I2-A. (6) kcal/mol. I2-A. I2 I2-A I2. I2 + A. 8.0. I2-A. Deactivation TBA. (2). Deactivation. TMG. TBA. I2. TBA. TMG. Deactivation. G. TEA. 15.3 TEA. 12.5kcal/mol TMG. TMG TEA TEA. TMG. (6). TMG. TMG. TEA. TEA. 3.5kcalmol. I2. I2. TEA. TMG. Deactivation. TMG. I2. (3). TIO. TIO. Activation. ISET. G. (TEA : 39.7 kcal/mol, TMG : 53.6kcal/mol) Set. I2. I2 TEA. Deactivation. I2-A. 93.8kcal/mol.

(107) 4.. (1) Activation (2) (3)Deactivation (4). ISET. SET I2-A. I-A, I2-A, I2 I2 A. P.

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(110) Pd Y=S 2-(2'-. Y=O. ). Pd. Y = NH. (1). Heck. 1. C2H2. Ph-Br. 13 PdII/PdIV. N-N. Pd0/PdII. Pd Pd Pd. 6. N-N, P-P. P-P. 22.6kcal/mol. Heck. Pd. 6. N-N Heck. Pd. P-P. N-N (1a) (1b). (2a). (2b) 7. RB ( 6. 7 ). 7. (7. 8). G. Reaction IV (P-I) (TMG). (TIO). (TEA). (A). Activation. ISET. SET. I2-A Deactivation. I-A, I2-A, I2. I2 I2 A. P.

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