寄稿論文鈴木－宮浦カップリング（SMC）反応の問題点| 東京化成工業

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1 Kumada- Corriu Stille egishi Suzuki- Miyaura iyama SMC one-pot SMC alkenyl-alkenyl Scheme 1 X Pd cat base (1979) X Pd cat base (1980) X Pd cat base (1981) X Pd cat base (1985) X Pd cat (1992) base X Pd cat Soderquist and (base) Fuerstner 1995 Scheme 1. 2

2 aryl-aryl Losartan (rck) anti-ms carbapenem (rck) CP-195,543 (Pfizer) UK-370,106 (Pfizer) MS-232,632 (ristol-myers Squibb) Valsartan (ovartis) Telmisartan (oehringer-ingelheim) LY- 451,395 (Eli Lilly) Irbesattan (Sanofi Aventis) Candesartan (Takeda) ASF SMC oscalid LED biaryl SMC SMC Pd i u Fe Pd Pd(0) Pd(II) Pd(0) Pd(II) Pd Scheme 2 Pd 2 (dppf) Pd(0): Pd(P 3 ) 4, Pd 2 (dba) 3, Pd/C Pd(II): Pd 2 (dppf), Pd 2 (PCy 3 ) 2, Pd 2 [P(o-tolyl) 3 ] 2, Pd 2 (P 3 ) 2, Pd(Ac) 2, Pd 2 [P(C F 102 ) 3 ] 2, Pd 2 [P(C F 102 ) 3 ] 2 i(ii): i 2 (dppf), i 2 (P 3 ) 2, i 2, ii 2 uthenium: supported on alumina Scheme 2. Catalyst system. 1-alkenyl 1-aryl 1-alkynyl allyl benzyl- Pd(P 3 ) 4 - alkylboron Scheme 3 Scheme 14 Pd Pd 2 (dppf) Scheme 4 3

3 1 3 Pd(P ) 4 4 X 2 base : 1-Alkenyl, 1-Aryl, 1-Alkynyl, Allyl, enzyl 4 X : Alkyl Pd(P 3 ) 4 Pd 2 (dppf) base base no reaction 4 Scheme 3. Pd 2 (dppf). Pd 2 (dppf) (3 mol%) I C 8 17 C 8 17 a / TF, reflux 98 % r Pd 2 (dppf) (3 mol%) a / TF, reflux 88 % r (C 2 ) 3 (C 2 ) 3 87 % r C 8 17 Pd 2 (dppf) (3 mol%) a / TF, reflux C % Scheme 4. Coupling reaction of alkylboron compounds. polycyclic ether gambierol gymnocin-a Scheme 5 Scheme 6 1 P P Tf 2 Pd(0) aq. base hydroboration P 2. oxidation 1 P 2 acetal formation 1 2 Scheme 5. 4

4 C Gambierol Gymnocin-A Scheme 6. SMC Pd Pd aryl tosylate mesylate chloride i Percec i 2 (dppf) Zn mesylate Scheme 7 educing agent: Zn i(ii) Zn i(0) i 2 (dppf) (10 mmol%) () 2 Ms Zn K 3 P 4 (3 equiv) dioxane, 100 C, 24 h 81 % Scheme 7. uli Table 1 mesitylboronic acid Scheme 8 Table 1. Coupling reaction of aryl chlorides. () 2 Z i 2 (dppf) (10 mol%) 4uLi K 3 P 4, dioxane, 80 C Z chloroarene catalyst/ time (h) product yield (%) -Ar - i 2 (dppf)/16 74 C Pd(P 3 ) 4 /16 C i 2 (dppf)/24 Pd(P 3 ) 4 /16 i 2 (dppf)/24 Pd(P 3 ) 4 / <

5 () 2 C i 2 (dppf) dppf/4uli C K 3 P 4 n 2 benzene 78 % 70 C, 16 h () 2 () 2 2 i 2 (dppf) dppf/4uli K 3 P 4 n 2 dioxane 80 C, 16 h 30 % 2 i 2 (dppf) 2 Sb 3 /4uLi K 3 P 4 n 2 benzene 70 C, 16 h 22 % Scheme 8. Indolese i Scheme 9 Scheme 10 ' () 2 i 2 (dppf) ' " K 3 P 4 dioxane, 95 C () 2 C C 100 % () 2 C C % () 2 C C Scheme 9. 0 % C () 2 i 2 (P 3 ) 2 /2P 3 K 3 P 4 n 2 toluene, 80 C C 97 % () 2 i 2 (P 3 ) 2 /2P 3 K 3 P 4 n 2 toluene, 80 C 99 % () 2 i 2 (P 3 ) 2 /2P 3 K 3 P 4 n 2 toluene, 100 C Scheme % 6

6 alkyl halide areneboronic acid i Scheme 11 Scheme 12 r () 2 ligand: bathophenanthroline i(cod) 2 ligand Kt-u 2-u 60 C, 5 h 91 % : no reaction Scheme 11. n-c X () 2 i(cod) 2, ligand n-c 8 17 K 3 P 4, 80 C, 2 h dimethyl acetamide ligand product yield (%) X = r X = Scheme 12. phosphine ligand i aryl iodide bromide boronic acid Scheme 13 X () 2 i K 3 P 4 dioxane, 130 C I () 2 65 % r () 2 74 % C r () 2 C 87 % I () 2 (Aryl chlorides, not effective) 6 % Scheme 13. 7

7 vinyl-vinyl coupling Scheme 14 SMC vinylboron vinylalkoxy boron vinylpalladium halide vinylpalladium alkoxide Scheme 14 X Pd(0) " oxidative addition reductive elimination " 'a PdX displacement transmetalation Pd '' " ' Pd' " ' ax Scheme 14. rown SMC Kumada (Mg) egishi (Zn) Stille (Sn) SMC phosphine arsine Scheme 15 P: P 3, dppf, dba, bda, P(t-u) 3 (Fu's ligand), PCy 3, biphenylphosphines (uchwald's ligand), phosphine oxide As: As 3 Scheme 15. aryl-aryl coupling aryl iodide bromide triflate arylboronic acid biaryl aryl chloride chloride chloride MIT Fu uchwald 8

8 Fu Pd(0) alkyl phosphine ligand activated aryl chloride Scheme 16 unactivated aryl chloride Scheme 17 Activated Aryl Chlorides: () 2 ' Pd 2 (dba) 3 P(t-u) 3 ' KF, TF, rt C () 2 C () 2 99 % Scheme % Unactivated Aryl Chlorides: () 2 Pd 2 (dba) 3 ' P(t-u) 3 ' KF, TF C () 2 88 % () 2 75 % Scheme 17. biaryl Fu Table 2 Table 2. Preparation of sterically hindered biaryls. Aryl alide oronic Acid Product Conditions Yield (%) () 2 1.5% Pd 2 (dba) 3 4.2% PCy 3, KF 60 C 89 r () 2 0.5% Pd 2 (dba) 3 1.2% P(t-u) 3, KF rt 98 9

9 uchwald dialkylbiaryl phosphine SMC o-(di-tert-butylphosphino)biphenyl Pd(Ac) 2 Scheme 18 Ligand: P(t-u) 2 () 2 Pd(Ac) 2 ' Ligand ' KF TF () 2 96 % 2 () % Scheme 18. uchwald Sphos Xphos Sphos aryl-aryl coupling Scheme 19 Sphos-Pd P Pd uchwald Pd pinacol arylboronate Scheme 20 ew Ligands PCy 2 PCy 2 Sos Xos indered Suzuki Coupling Using Ligand, Sos catalyst, Pd 2 (dba) 2 / ligand, Sos, L : Pd = 2 :! ; K 3 P 4 ; toluene mol% Pd 0,1 r () C, 12 h 96 % r () 2 mol% Pd C, 18 h 82 % Scheme

10 Suzuki Coupling at Low Catalyst loading Using Ligand Sos catalyst, Pd(Ac) 2 ; ligand, Sos; L:Pd = 2.5:1; K 3 P 4 ; toluene alide oronic acid Product mol% Pd Conditions Yield (%) t-u r () 2 t-u r r () C, 1.5 h C, 24 h C, 16 h 97 t-u () 2 n-u C, 10 h C, 24 h 93 Suzuki Coupling of Pinacol Aryl oronates Using Ligand Sos S 1% Pd(Ac) 2. 2% Sos K 3 P 4, toluene- 2 (10:1) rt, 24 h Scheme 20. S 91 % Martin uchwald Pd SMC dialkylbiarylphosphine Scheme 21 * Substituent fixes confomation of 2 P over bottom ring, enhancing rate of reductive elimination * 1, 2 = prevents cyclometallation, increasing stability * 1, 2 = large group (e.g. isopropyl) increases [L 1 Pd(0)] 4 P * = Usually only for ease of synthesis (e.g. Xos) * Alkyl groups increase electron density at P, increasing rate of oxidative addition * Increased size of enhances rate of reductive elimination * Large increases [L 1 Pd(0)]. = Cy usually better for than = t-u for high turnover number Lower aryl ring * Increases size of ligand, slowing rate of oxidation by 2 * Allows stabilizing Pd-arene interactions * Promotes reductive elimination Scheme 21. Structural features of the dialkylbiarylphosphines and their impact on the efficacy of catalysts using these ligands. tetraphenyl phosphine aryl chloride phosphine bowl-shape 11

11 Fu uchwald SMC phosphine oxide Scheme 22 t-u t-u P 3 /Et 3 C 2 2 t-u P t-u 2 t-u P t-u Air-stable phosphine oxide Aryl chloride Arylboronic acid Product Yield(%) () 2 93 () 2 95 eaction conditions: Pd(dba) 2, Kt-u, ligand and TF Scheme 22. Air-stable phosphine oxide ligand. Mohanty 1,4-bis(2-hydroxy-3,5-ditert-butylbenzyl)piperazine SMC Pd aryl-aryl coupling Pd/C a 3 P 4-50% heteroaryl-aryl heteroaryl-heteroaryl coupling coupling partner -heterocyclic carbene (C) ligand C C SMC organoborane organoboronic acid organoboronate ester organotrifluoroborate C- hydroboration Scheme 23 12

12 C C 2 C 2 C 2 -- C C E- C Cr (Sia) 2 r (SIa) 2 t-uli (Sia) 2 Z- Scheme 23. SMC coupling partner 1- alkenylborane 1-alkenyl halide conjugated alkadiene cis-vinylborane Table 3 siamyl 1-alkenyl halides organoboronic acids organoboronate esters Table 3. Vinyl-vinyl coupling reactions. 1-Alkenylborane u u 1-Alkenyl romide Product Yield (%) [Purity (%)] b) r 86 [98] u u u a) r 49 [99] u r u a) 42 [89] ex b) r ex 88 [99] u u r ex u a) 49 [98] ex b) r 89 [98] eaction conditions: 1-3 mol % of Pd(P 3 ) 4 / aet / enzene / eflux 2h a) Disiamyl b) 1,3,2-enzodioxaboryl Grignard Scheme 24 13

13 i. y transmetalation (Grignard reagents and organolithium compounds) ArMgX 3 () 3 Ar() 2 ii. y hydroboration C C C C r 2 S 2 2 / Scheme 24. () 2 Table 3 cis-vinylborane vinyl halides coupling partner boronate ester conjugated alkadiene Table 4 Table 4. Coupling reaction of cis-1-alkenylboron compounds. Pd(P u Y 3 ) 4 2 X aet / benzene reflux, 2 h u Y 2 X Product Yield (%) Purity (%) (Sia) 2 u 49 () r ex 2 ex 87 >98 >99 (Sia) 2 58 >94 ( ) 2 I u 49 >83 () 2 98 >97 (Sia) 2 u 54 >92 I () 2 87 >99 boronic acid boronate ester arylboronic acid aryl halide Pd biaryl biaryl Ullmann biaryl SMC biaryl 14

14 Thompson mesitylboronic acid biaryl mesitylene Scheme 25 r () 2 C Pd(P 3 ) 4 aq a 2 C 3 benzene, reflux C Thompson 1984 C r Pd(P 3 ) 4 C C S () 2 S aq a 2 C 3 benzene, reflux S S S Gronowitz 1987 very small major Scheme 25. Gronowitz formyl thiopheneboronic acid bithiophenyl thiophene aldehyde Scheme 25 aryl-aryl-smc biaryl arylboronic acid arylboronic acid aryl-aryl coupling arylboronic acid Table 5 Table 5. Coupling reaction of sterically hindered areneboronic acid. () 2 I Pd(P 3 ) 4 base Solvent ase Product yield (%) [Yield of mesitylene (%)] eac. time: 8 h 24 h 48 h enzene / 2 a 2 C 3 25 [ 6 ] 77 [ 12 ] 85 [ 26 ] a() 2 Tl 92 [ 13 ] 91 [ 20 ] DME / 2 a 2 C 3 50 [ 1 ] 66 [ 2 ] 83 [ 7 ] K 3 P 4 70 [ 0 ] 83 [ 3 ] a() 2 99 [ 2 ] 15

15 coupling partner boronate ester arylboronic acid Table 6 arylboronic acid Table 7 Table 6. Coupling reaction using sterically hindered areneboronic ester. () 2 I Pd(P 3 ) 4 ase s() 2 u Solvent ase Yied / % a DMF / 100 C Cs 2 C 3 87 (3) -(C 2 ) 3 - DMF / 100 C Cs 2 C 3 K 3 P 4 98 (4) 98 (2) a GLC yields of the biaryl after 8 h, and the formation of mesitylene is shown in the parentheses. Table 7. Coupling of areneboronic esters having electron-withdrawing functional group. () 2 I Pd(P 3 ) 4 C C C () 2 Solvent / reac. temp. ase Product yield (%) [enzaldehyde yield (%)] () 2 DME- 2 / 80 C a 2 C 3 60 [ 43 ] () 2 DME- 2 / 80 C Cs 2 C 3 75 [ 34 ] -(C 2 ) 3 - DMF / 100 C Cs 2 C 3 98 [ 12 ] arylboronate ester SMC boronate ester pri- sec- tert-alcohol ester pri- sec- tert- tert-butyl boronate boronate ester deboronation pri- sec- tert- deboronation tert-alcohol boronate sec-alcohol boronate Table 4 pinacolboronate (tert-alcohol boronate) bis(pinacolato)diboron aryl halide alkenyl halide Pd 2 (dppf) pinacol boronate Scheme 26 16

16 Ar-X or Ar-Tf Pd 2 (dppf) AcK / DMS 80 C Ar X, Tf Pd 2 (P 3 ) 2 K / toluene 50 C Scheme 26. bis(pinacolato)diboron pinacolborane Scheme 27 Ar-X or Ar-Tf Pd 2 (dppf) Et 3 / dioxane 80 C Ar X, Tf Pd 2 (dppf) Et 3 / dioxane 80 C Scheme 27. pinacolborane - hydroboration Ma aryl iodide Pd CuI (10%) a aryl bromide SMC boronate boronic acid coupling partner arylboronic acid deboronation coupling partner arylboronic acid aryl halide triflate Scheme 28 () 2 r Pd(0) base X () 2 Pd(0) base Scheme

17 Molander organotrifluoroborate Scheme 29 SMC SMC 1. Via Grignards or rganolithiums MgX or Li KF 2 () 3 aq. acetone F 3 K 2. Via ydroboration KF 2 aq. acetone F 3 K Scheme 29. SMC alkyl-alkenyl coupling Scheme 30 alkyl-aryl coupling Scheme 30 Et 2 C Et 2 C z F 3 K 6 Tf Pd 2 (dppf) C 2 2 Cs 2 C 3, TF/ 2 z 6 68 % F 3 K r C Pd 2 (dppf) C 2 2 Cs 2 C 3, TF/ 2 C Scheme % one-pot trisubstituted conjugated diene Scheme 31 r r F 3 K Pd(P 3 ) 4, Cs 2 C toluene/ 2 60 C, 2 h r C 2 F 3 K (one pot) 80 C, 2.5 h C 2 89 % Scheme

18 aryltrifluoroborate aryl halide biaryl Scheme 32 Ac F 3 K r C Pd(Ac) 2, P 3 K 2 C 3, Ac 70 % C Pd(Ac) 2 F 3 K r C K 2 C 3, C 99 % C Pd(Ac) 2 C F 3 K r K 2 C 3, 89 % Pd(Ac) 2 F 3 K r K 2 C 3, 95 % Scheme 32. alkynyltrifluoroborate Scheme 33 Scheme 34 1) n-uli (1 equiv) F 3 K 2) () 3 (1.5 equiv) 3) KF 2 n-u n-c 8 17 (C 2 ) 2 TDMS(C 2 ) 2 TMS Yield (%) Scheme 33. Pd 2 (dppf) C 2 2 n-u F 3 K X Ar Cs 2 C 3, solvent n-u Ar solvent: A = TF = TF/ 2 n-u n-u n-u n-u 2 2 Ac A, 98 %, X=Tf A, 33 %, X=r, 61 %, X=r A, 87 %, X=Tf A, 59 %, X=r A, 30 %, X=I A, 40 %, X=, 39 %, X=r Scheme

19 organotrifluorborate SMC boronic acid boronate ester Molander SMC Table 8 ester Table 9 Table 8. SMC reaction of reactants sensitive to base-1. r (C 2 ) 10 C 2 Pd 2 (dppf) (C 2 ) 10 C 2 Solvent ase (equiv.) Temp. / C Time / h Yield / % DMF K 2 C 3 (4) DMF KAc (4) DMF K 2 C 3 (2) C 3 C K 2 C 3 (4) DMF K 3 P 4 (4) Table 9. SMC reaction of reactants sensitive to base-2. alide orane Product Yield / % r (C 2 ) 7 C 3 (C 2 ) 7 C 3 95 (C 2 ) 10 C 2 C 3 88 r (C 2 ) 10 C 2 C 3 C 3 (C 2 ) 10 C 2 C 3 84 r (C 2 ) 10 C 2 C 3 Isolated yields based on halides. Pd 2 (dppf) (3 mol%) / K 2 C 3 / DMF 20

20 SMC SMC aryl halide boronic acid combinatorial SMC Leadbeater Kabalka SMC Pd organoboronic acid boronate ester SMC 1) A. Suzuki, Proc. Jpn. Acad. 2004, 80, ) A. Suzuki, Chem. Commun. 2005, ),, 2005, 63, ) T. ayashi, M. Konishi, Y. Kobori, M. Kumada, T. iguchi, K. irotsu, J. Am. Chem. Soc. 1984, 106, ) M. Sasaki, ull. Chem. Soc. Jpn. 2007, 80, ) V. Percec, J-Y. ae, J. rg. Chem. 1995, 60, ) S. Saito, M. Sakai,. Miyaura, Tetrahedron Lett. 1996, 37, ) S. Saito, S. htani,. Miyaura, J. rg. Chem. 1997, 62, ) A. F. Indolese, Tetrahedron Lett. 1997, 38, ) K. Inada,. Miyaura, Tetrahedron 2000, 56, ) J. S. Zhou, G. C. Fu, J. Am. Chem. Soc. 2004, 126, ) Sumitomo Chem. Tokukai , ) D. Zim, L. Monteiro, Tetrahedron Lett. 2002, 43, ). Miyaura, K. Yamada,. Suginome, A. Suzuki, J. Am. Chem. Soc. 1985, 107, ) A. A. C. rago,.. Morgan,. Ujaque, F. Maseras, J. Am. Chem. Soc. 2005, 127, ) C. M. unes, A. L. Monteiro, J. raz. Chem. Soc. 2007, 18, ) G. Espino, A. Kurbangalieva, J. M. rown, Chem. Commun. 2007, ) T. Yanagi,. Miyaura, A. Suzuki, Synth. Commun. 1981, 11, ) A. F. Littke, C. Dai, G. C. Fu, J. Am. Chem. Soc. 2000, 122, ) J. P. Wolfe,. A. Singer,.. Yang, S. L. uchwald, J. Am. Chem. Soc. 1999, 121, ) T. E. arder, S. D. Walker, J.. Martinelli, S. L. uchwald, J. Am. Chem. Soc. 2005, 127, ). Martin, S. L. uchwald, Acc. Chem. es. 2008, 41, ) T. Iwasaki, T. Komano, A. Tajima, M. Tokunaga, Y. bora, T. Fujihara, Y. Tsuji, rganometallics 2006, 25, ). hta, M. Tokunaga, Y. bora, T. Iwai, T. Iwasaki, T. Fujihara, Y. Tsuji, rg. Lett. 2007, 9, ) L. Ackermann,. orn, Angew. Chem. Int. Ed. 2005, 44, ) S. Mohanty, D. Suresh, M. S. alakrishna, J. T. Mague, Tetrahedron 2008, 64, ) a) T. Maegawa, Y. Kitamura, S. Sako, T. Udzu, A. Sakurai, A. Tanaka, Y. Kobayashi, K. Endo, U. ora, T. Kurita, A. Kozaki, Y. Monguchi,. Sajiki, Chem. Eur. J. 2007, 13, 5937; b) Y. Kitamura, S. Sako, T. Udzu, A. Tsutsui, T. Maegawa, Y. Monguchi,. Sajiki, Chem. Commun. 2007, ) C. Pan, M. Liu, L. Zhang,. Wu, J. Ding, J. Cheng, Catalysis 2008, 9, ) a).. Taylor, F. X. Felpin, rg. Lett. 2007, 9, 2944; b) S. Li, Y. Lin, J. Cao, S. Zhang, J. rg. Chem. 2007, 72, 4067; c) Y.. Fang,. Karisch, M. Lautens, J. rg. Chem. 2007, 72,

21 30). Miyaura, M. Satoh, A. Suzuki, Tetrahedron Lett. 1986, 27, ) T. Yanagi,. Miyaura, A. Suzuki, Synth. Commun. 1981, 11, ) W. J. Thompson, J. Gaudino, J. rg. Chem. 1984, 49, ) S. Gronowitz, Chem. Scripta. 1987, 27, ) T. Watanabe,. Myaura, A. Suzuki, Synlett 1992, ) a) T. Ishiyama,. Miyaura, J. rg. Chem. 1995, 60, 7508; b) T. Ishiyama, Y. Itoh, T. Kitano,. Miyaura, Tetrahedron Lett. 1997, 38, ) J. Takagi, K. Takahashi, T. Ishiyama,. Miyaura, J. Am. Chem. Soc. 2002, 124, 8001, 37),, 1999, 57, ) a) M. Murata, S. Watanabe, Y. Masuda, J. rg. Chem. 1997, 62, 6458; b) M. Murata, T. yama, S. Watanabe, Y. Masuda, J. rg. Chem. 2000, 65, 164; c) M. Murata, T. yama, S. Watanabe, Y. Masuda, Synthesis 2000, ) W. Zhu, D. Ma, rg. Lett. 2008, 8, ) G. Molander, T. Ito rg. Lett. 2001, 3, ) a) G. Molander, C-S. Yun, M. ibagorda,. iolatto J. rg. Chem. 2003, 68, 5534; b) G. A. Molander, M. ibagorda J. Am. Chem. Soc. 2003, 125, ) G. A. Molander, Y. Yokoyama J. rg. Chem. 2006, 71, ) a) G. A. Molander,. Figueroa, Aldrichimica Acta 2005, 38, 49; b) G. A. Molander, D. E. Petrillo,.. Landzberg, J. C. ohanna,. iolatto, Synlett 2005, ) G. A. Molander,. W. Katona, F. Machrouhi, J. rg. Chem. 2002, 67, ) G. A. Molander,. Ellis, Acc. Chem. es. 2007, 40, ) S. Abe,. Miyaura, A. Suzuki, ull. Chem. Soc. Jpn. 1992, 65, ). E. Leadbeater, Chem. Commun. 2005, ) G. W. Kabalka,. M. Pagni, C. M. air, rg. Lett. 1999, 1, (eceived Jan. 2009) 22

22 Fe P Pd 2 P. C 2 2 [1,1'-is(diphenylphosphino)- ferrocene]palladium(ii) Dichloride Dichloromethane Complex (1:1) 1g 5g 25g [2064] (o-tol) 3 P Pd 2 (o-tol) 3 P is(tri-o-tolylphosphine)- palladium(ii) Dichloride 1g [2026] 3 P Pd 2 3 P is(triphenylphosphine)- palladium(ii) Dichloride 1g 5g 25g [1667] P Fe i 2 P [1,1'-is(diphenylphosphino)- ferrocene]nickel(ii) Dichloride 1g 5g [2226] 3 P i 2 3 P Cy 3 P Pd 2 Cy 3 P is(tricyclohexylphosphine)- palladium(ii) Dichloride 1g 5g [2055] (Ac) 2 Pd Palladium(II) Acetate 1g, 5g [A1424] Pd Pd ( 3 P) 4 Pd is(triphenylphosphine)- nickel(ii) Dichloride 10g, 100g [1571] Tris(dibenzylideneacetone)- dipalladium(0) 1g, 5g [T2184] Tetrakis(triphenylphosphine)- palladium(0) 1g, 5g, 25g [T1350] Fe P 2 P 2 P(t-u) 2 t-u t-u P t-u Tri-tert-butylphosphine 5g [T1912] 1,1'-is(diphenylphosphino)- ferrocene 1g, 5g, 25g [2027] 2-(Di-tert-butylphosphino)- biphenyl 1g [D3387] As Triphenylarsine 5g, 25g [T0508] is(pinacolato)diboron 1g, 5g, 25g [1964] is(neopentyl Glycolato)diboron 1g [2254] 23

TCIメール No.142 | 東京化成工業

TCIメール No.142 | 東京化成工業 Kumada- Corriu Stille egishi Suzuki- Miyaura iyama SMC one-pot SMC alkenyl-alkenyl Scheme 1 X Pd cat base (1979) X Pd cat base (1980) X Pd cat base (1981) X Pd cat base (1985) X Pd cat (1992) base X Pd

寄稿論文 鈴木－宮浦カップリング（SMC）反応の問題点| 東京化成工業

寄稿論文鈴木－宮浦カップリング（SMC）反応の問題点| 東京化成工業