Efficient Intramolecular C–H Insertion Catalyzed by Iridium Porphyrin Complexes

Cristóbal López-Sánchez; Míriam Álvarez-Corral; Manuel Muñoz-Dorado; Ignacio Rodríguez-García

doi:10.1055/s-0032-1317296

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(17): 2469-2472
DOI: 10.1055/s-0032-1317296

letter

Efficient Intramolecular C–H Insertion Catalyzed by Iridium Porphyrin Complexes

Cristóbal López-Sánchez

Department of Organic Chemistry, University of Almería, 04120 Almería, Spain Fax: +34(950)015481 eMail: irodrigu@ual.es

,

Míriam Álvarez-Corral

Department of Organic Chemistry, University of Almería, 04120 Almería, Spain Fax: +34(950)015481 eMail: irodrigu@ual.es

,

Manuel Muñoz-Dorado

Department of Organic Chemistry, University of Almería, 04120 Almería, Spain Fax: +34(950)015481 eMail: irodrigu@ual.es

,

Ignacio Rodríguez-García*

Department of Organic Chemistry, University of Almería, 04120 Almería, Spain Fax: +34(950)015481 eMail: irodrigu@ual.es

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Octaethylporphyrin and tetraphenylporphyrin Ir(I) and Ir(III) complexes are useful catalysts for intramolecular C–H insertion processes of stabilized diazo compounds. While the Ir(I) complex TPP[Ir(CO)₃]₂ is the most efficient and selective catalyst, the others afford mixtures of cyclization and dimerization products. The effect of the solvent polarity on the selectivity of the reaction is also presented.

Key words

iridium complexes - porphyrins - diazo compounds - carbene complexes - intramolecular C–H insertion

Volltext

Referenzen

References
1 Sakaguchi S, Yamaga T, Ishii Y. J. Org. Chem. 2001; 66: 4710
2 Tani K, Iseki A, Yamagata T. Chem. Commun. 1999; 1821
3 Malacea R, Poli R, Manoury E. Coord. Chem. Rev. 2010; 254: 729
4 Tejel C, Ciriano MA In Organometallic Oxidation Catalysis . 22 ed., Meyer F, Limberg C. Springer; Berlin: 2007: 97
5 Helmchen G, Dahnz A, Duebon P, Schelwies M, Weihofen R. Chem. Commun. 2007; 675
6 Takeuchi R, Kezuka S. Synthesis 2006; 3349
7 Teichert JF, Fananas-Mastral M, Feringa BL. Angew. Chem. Int. Ed. 2011; 50: 688
8 Kezuka S, Okado T, Niou E, Takeuchi R. Org. Lett. 2005; 7: 1711
9 Fujihara T, Iwai T, Terao J, Tsuji Y. Synlett 2010; 2537
10 Onodera G, Toeda T, Toda NN, Shibagishi D, Takeuchi R. Tetrahedron 2010; 66: 9021
11 Kuninobu Y, Asanoma D, Takai K. Synlett 2010; 2883
12 Davies HM. L, Manning JR. Nature (London) 2008; 451: 417
13 Slattery CN, Ford A, Maguire AR. Tetrahedron 2010; 66: 6681
14 Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010; 110: 704
15 Davies HM. L, Loe O. Synthesis 2004; 2595
16 Davies HM. L. Angew. Chem. Int. Ed. 2006; 45: 6422
17 Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861
18 Grohmann M, Maas G. Tetrahedron 2007; 63: 12172
19 Davies HM. L, Thompson JL Abstracts of Papers, 229th ACS National Meeting, San Diego, USA, March 13-17, 2005; Abstract ORGN-089
20 Lovely CJ In Silver in Organic Chemistry . Harmata M. John Wiley & Sons; New York: 2010: 229
21 Liu XJ, Hamilton IP, Han KL, Tang ZC. Phys. Chem. Chem. Phys. 2010; 12: 10602
22 Mbuvi HM, Woo LK. Organometallics 2008; 27: 637
23 Mbuvi HM, Woo LK. J. Porphyrins Phthalocyanines 2009; 13: 136
24 Fructos MR, Belderrain TR, de Fremont P, Scott NM, Nolan SP, Diaz-Requejo MM, Perez PJ. Angew. Chem. Int. Ed. 2005; 44: 5284
25 Hansen J, Autschbach J, Davies HM. L. J. Org. Chem. 2009; 74: 6555
26 Suematsu H, Katsuki T. J. Am. Chem. Soc. 2009; 131: 14218
27 Yasutomi Y, Suematsu H, Katsuki T. J. Am. Chem. Soc. 2010; 132: 4510
28 Ichinose M, Suematsu H, Yasutomi Y, Nishioka Y, Uchida T, Katsuki T. Angew. Chem. Int. Ed. 2011; 50: 9884
29 Zhou CY, Huang JS, Che CM. Synlett 2010; 2681
30 Thu HY, Tong GS.-M, Huang JS, Chan SL.-F, Deng QH, Che CM. Angew. Chem. Int. Ed. 2008; 47: 9747
31 Callot HJ, Metz F. Tetrahedron Lett. 1982; 23: 4321
32 Cheung CW, Chan KS. Organometallics 2008; 27: 3043
33 Hoyano JK, Graham WA. G. J. Am. Chem. Soc. 1982; 104: 3723
34 Janowicz AH, Bergman RG. J. Am. Chem. Soc. 1982; 104: 352
35 Hoyano JK, McMaster AD, Graham WA. G. J. Am. Chem. Soc. 1983; 105: 7190
36 Bianchini C, Masi D, Meli A, Peruzzini M, Sabat M, Zanobini F. Organometallics 1986; 5: 2557
37 Viciano M, Poyatos M, Sanau M, Peris E, Rossin A, Ujaque G, Lledos A. Organometallics 2006; 25: 1120
38 Feller M, Karton A, Leitus G, Martin JM. L, Milstein D. J. Am. Chem. Soc. 2006; 128: 12400
39 Conejero S, Paneque M, Poveda ML, Santos LL, Carmona E. Acc. Chem. Res. 2010; 43: 572
40 Del Rossi KJ, Zhang XX, Wayland BB. J. Organomet. Chem. 1995; 504: 47
41 Wang JC, Xu ZJ, Guo Z, Deng QH, Zhou CY, Wan XL, Che CM. Chem. Commun. 2012; 48: 4299
42 Kanemitsu H, Harada R, Ogo S. Chem. Commun. 2010; 46: 3083
43 Bhagan S, Wayland BB. Inorg. Chem. 2011; 50: 11011
44 Ye T, McKervey MA. Chem. Rev. 1994; 94: 1091
45 Saito H, Oishi H, Kitagaki S, Nakamura S, Anada M, Hashimoto S. Org. Lett. 2002; 4: 3887
46 Procedure for Intramolecular C _sp ³–H Insertion Reaction: The catalyst (5% mmol) was added to a solution of diazo compound 1 (0.2 mmol) in anhyd solvent (10 mL/mmol) under a nitrogen atmosphere. The reaction was monitored by TLC until completion. Next, the solvent was removed at reduced pressure and the residue was chromatog-raphed (SiO₂), eluting with a mixture of hexane–Et₂O (98:2). Compounds 2 and 3 were obtained in different relations and yields (see Table 1).
47 Spectroscopic Data of Dimethyl 2,3-Bis[2-(benzyloxy)-phenyl]maleate (3): IR(film): 1010, 1110, 1273, 1595, 1664, 1737, 2851, 2920 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 3.35 (s, 3 H, CO₂Me), 5.11 (s, 2 H, OCH₂Ph), 7.08 (m, 2 H, H6, H4), 7.55 (m, 5 H, H2′–H6′), 7.61 (dt, ³ J = 7.5 Hz, ⁴ J = 1.9 Hz, 1 H, H5), 7.93 (dd, ³ J = 7.8 Hz, ⁴ J = 1.9 Hz, 1 H, H3). ¹³C NMR (75 MHz, CDCl₃): δ = 51.84 (Me, CO₂Me), 71.18 (OCH₂Ph), 112.65 (CH, C6), 121.43 (CH, C4), 122.68 (C, C2), 128.47–128.66 (CH, C2′,C3′,C4′), 130.91 (CH, C3), 133.98 (C, C=C), 135.10 (C, C1′), 136.32 (CH, C5), 159.41 (C, C1), 165.41 (CO₂Me).
48 Representative Procedure of the Synthesis of Iridium Porphyrin Complexes:⁵⁰ A mixture of (TPP)H₂ (39 mg, 0.06 mmol) and [Ir(CO)₃Cl]₂ (20 mg, 0.06 mmol) in xylene (3 mL) was stirred at reflux temperature for 15 h under a N₂ atmosphere. The resulting solution was evaporated at reduced pressure and the residue was chromatographed on a silica gel column with several solvent mixtures to afford three fractions. The first one (hexane–Et₂O, 9:1), was non-reacted tetraphenylporphyrin, which could be recycled. The second fraction (toluene–acetone, 3:1) was a brown-red solid, and the third fraction a purple solid. This was recrystallized in EtOH to afford the iridium(III) complex 7. The second fraction (brown-red solid) was recromatographed with different mixtures of toluene and acetone (100:0, 95:5, 8:2, 6:4 and 1:1) affording a red solid which was identified as the iridium(I) complex 5.
49 Spectroscopic data of OEP[Ir(CO)₃]₂ (4) have been described previously.^{50 14}N NMR (36.15 MHz, CDCl₃): δ = 263.92. Spectroscopic data of TPP[Ir(CO)₃]₂ (5): IR (film): 2923, 2852, 2052, 1982, 1596, 1441, 1357, 1073, 1017 cm^–1. HRMS (FAB): m/z [M + H]⁺ calcd for C₅₀H₂₈N₄O₆Ir₂: 1166.1267; found: 1166.3176. ¹H NMR (300 MHz, CDCl₃): δ = 7.81 (m, 3 H, H3′, H4′, H5′), 8.15 (m, 2 H, H2′, H6′), 8.90 (br s, 2 H, H_β). ¹³C NMR (75 MHz, CDCl₃): δ = 123.18 (C, C _meso ), 124.35 (CH, C3′, C4′, C5′), 124.72 (CH, C2′, C6′), 129.32 (CH, C_β), 135.59 (C, C1′), 201.53 (C, C=O). ¹⁴N NMR (36.15 MHz, CDCl₃): δ = 264.08. Spectroscopic data of OEP[Ir(CO)Cl] (6) have been described previously.^{50 14}N NMR (36.15 MHz, CDCl₃): δ = 264.01. Spectroscopic data of TPP[Ir(CO)Cl] (7): IR (film): 2962, 2059, 1259, 1173, 1017, 870 cm^–1. HRMS (FAB): m/z [M + H]⁺ calcd for C₄₅H₂₉N₄OClIr: 869.1654, found: 869.1622. ¹H NMR (300 MHz, CDCl₃): δ = 7.78 (m, 3 H, H3′, H4′, H5′), 8.21 (m, 2 H, H2′, H6′), 8.82 (br s, 2 H, H_β). ¹³C NMR (75 MHz, CDCl₃): δ = 118.14 (C, C _meso ), 124.72 (CH, C3′, C4′, C5′), 125.75 (CH, C2′, C6′), 132.48 (CH, C_β), 140.43 (C, C1′). ¹⁴N NMR (36.15 MHz, CDCl₃): δ = 264.2.
50 Ogoshi H, Setsune J, Yoshida Z. J. Organomet. Chem. 1978; 159: 317
51 Kadish KM, Deng YJ, Yao CL, Anderson JE. Organometallics 1988; 7: 1979
52 Schrock RR, Osborn JA. J. Am. Chem. Soc. 1971; 93: 3089
53 Suematsu H, Kanchiku S, Uchida T, Katsuki T. J. Am. Chem. Soc. 2008; 130: 10327