메뉴 건너뛰기




Volumn 27, Issue 17, 2008, Pages 4300-4309

Heterolytic splitting of allylic alcohols with palladium(O)-TPPTS in water. Stabilities of the allylphosphonium salt of TPPTS and of the ionic complex [Pd(η-allyl)(TPPTS)2]+

Author keywords

[No Author keywords available]

Indexed keywords

CHLORINE COMPOUNDS; IONIZATION OF LIQUIDS; PALLADIUM;

EID: 52649110618     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om701273j     Document Type: Article
Times cited : (27)

References (78)
  • 1
    • 52649121226 scopus 로고    scopus 로고
    • Kuntz, E. G, Rhône-Poulenc Ind, French Patent 2 314 910, June 25, 1975
    • Kuntz, E. G. (Rhône-Poulenc Ind.), French Patent 2 314 910, June 25, 1975.
  • 3
    • 0001220727 scopus 로고
    • (b) Kuntz, E. G. CHEMTECH 1987, 17, 570-575.
    • (1987) CHEMTECH , vol.17 , pp. 570-575
    • Kuntz, E.G.1
  • 5
    • 52649141970 scopus 로고    scopus 로고
    • Jenck, J, Rhône-Poulenc Ind, French Patent 2 478 078, Dec 3, 1980
    • Jenck, J. (Rhône-Poulenc Ind.), French Patent 2 478 078, Dec 3, 1980.
  • 6
    • 52649131746 scopus 로고    scopus 로고
    • Cornils, B, Hibbel, J, Lieder, B, Much, J, Schmidt, V, Wiebus, E, Konkol, W, Ruhrchemie) U.S. Patent 4 523 036, Sep 18, 1982 prior German patent
    • Cornils, B.; Hibbel, J.; Lieder, B.; Much, J.; Schmidt, V.; Wiebus, E.; Konkol, W. (Ruhrchemie) U.S. Patent 4 523 036, Sep 18, 1982 (prior German patent).
  • 8
    • 52649140929 scopus 로고    scopus 로고
    • Kuntz, E. G, Rhône-Poulenc Ind, French Patent 2 366 237, July 27, 1976
    • (a) Kuntz, E. G. (Rhône-Poulenc Ind.) French Patent 2 366 237, July 27, 1976.
  • 9
    • 52649146875 scopus 로고    scopus 로고
    • Yochimura, N, Tamura, M, Kuraray) U.S. Patent 4 334 117, Sep 1, 1979 prior Japan patent
    • (b) Yochimura, N.; Tamura, M. (Kuraray) U.S. Patent 4 334 117, Sep 1, 1979 (prior Japan patent).
  • 10
    • 52649127734 scopus 로고    scopus 로고
    • Yochimura, N, Tamura, M, Kuraray U.S. Patent 4 356 333,March 28, 1980
    • (c) Yochimura, N.; Tamura, M. (Kuraray) U.S. Patent 4 356 333,March 28, 1980.
  • 11
    • 52649147405 scopus 로고    scopus 로고
    • Yochimura, N, Tamura, M, Kuraray U.S. Patent 4 417 079,Feb 16, 1982
    • (d) Yochimura, N.; Tamura, M.;(Kuraray) U.S. Patent 4 417 079,Feb 16, 1982.
  • 12
  • 15
    • 52649174740 scopus 로고    scopus 로고
    • Maeda, T, Tokitoh, Y, Yoshimura, N, Kuraray) Eur. Patent 0 296 550, June 24, 1987 (prior Japan patent, Allylic phosphonium salts of TPPMS substituents: allyl; 2,7-octadien-l-yl; 2-buten-l-yl
    • Maeda, T.; Tokitoh, Y.; Yoshimura, N. (Kuraray) Eur. Patent 0 296 550, June 24, 1987 (prior Japan patent). Allylic phosphonium salts of TPPMS (substituents: allyl; 2,7-octadien-l-yl; 2-buten-l-yl).
  • 22
    • 52649165009 scopus 로고
    • French Patent 2 652 514, June 22
    • (a) Sinou, D. French Patent 2 652 514, June 22, 1989.
    • (1989)
    • Sinou, D.1
  • 29
    • 52649153443 scopus 로고    scopus 로고
    • Grosselin, J, Kempf, H, Lecouve, J, Rhône-Poulenc Chimie) Eur. Patent 0 470 000 Al, Aug 2, 1990 prior French patent
    • Grosselin, J.; Kempf, H.; Lecouve, J. (Rhône-Poulenc Chimie) Eur. Patent 0 470 000 Al, Aug 2, 1990 (prior French patent).
  • 31
    • 4544248742 scopus 로고    scopus 로고
    • Dimethylallyl alcohol reacted with 4-bromotryptophan to give clavicipitic acid by a Heck reaction under highly basic conditions NaOH, but with NaOOCCH3, isoprenylation of 4-bromotryptophan occurred
    • (b) Yokoyama, Y.; Hikawa, H.; Mitsuhashi, M.; Uyama, A.; Hiroki, Y.; Murakami, Y. Eur. J. Org. Chem. 2004, 6, 1244-1253, Dimethylallyl alcohol reacted with 4-bromotryptophan to give clavicipitic acid by a Heck reaction under highly basic conditions (NaOH), but with NaOOCCH3, isoprenylation of 4-bromotryptophan occurred.
    • (2004) Eur. J. Org. Chem , vol.6 , pp. 1244-1253
    • Yokoyama, Y.1    Hikawa, H.2    Mitsuhashi, M.3    Uyama, A.4    Hiroki, Y.5    Murakami, Y.6
  • 32
    • 52649171803 scopus 로고    scopus 로고
    • French Patent 2 862 639, Nov 25
    • Kuntz, E. G.; Amgoune, A. French Patent 2 862 639, Nov 25, 2003.
    • (2003)
    • Kuntz, E.G.1    Amgoune, A.2
  • 38
    • 16244407390 scopus 로고    scopus 로고
    • (a) Muzart, J. Tetrahedron 2005, 61, 4179-4212.
    • (2005) Tetrahedron , vol.61 , pp. 4179-4212
    • Muzart, J.1
  • 42
    • 52649167687 scopus 로고    scopus 로고
    • Homologous Pt(η3-allyl)(TPPTS)2+ was recently prepared from PtCl2(TPPTS)2 and allyl alcohol with stoichiometric formation of 1-hydroxyacetone.26b We have shown that PtCl2(TPPTS)2 catalyzes a selective C-allylation of guaiacol with allyl alcohol into p-eugenol and o-eugenol (65/35) in water. 26c The selectivity of the PtCl2(TPPTS)2 catalyst in this allylation was similar to that obtained with the palladium(0) TPPTS catalyst.24
    • 24.
  • 44
    • 52649085165 scopus 로고    scopus 로고
    • Reference 17, patent example number 17
    • (c) Reference 17, patent example number 17.
  • 47
    • 52649137726 scopus 로고    scopus 로고
    • 3 solutions with chloride (chloride/Pd molar ratio 4) from potassium tetrachloropalladate(II) by the same method.
    • 3 solutions with chloride (chloride/Pd molar ratio 4) from potassium tetrachloropalladate(II) by the same method.
  • 49
    • 52649162244 scopus 로고    scopus 로고
    • With a Pd concentration of 0.011 M, the following values were obtained: n (TPPTS/Pd(0) ratio, 3, δ 23.85 ppm; n, 3.53, δ 21.75 ppm; n, 4.06, δ 17.97 ppm; n, 8, δ 2.06 ppm (TPPTS alone: δ-5 ppm, This variation allows an estimation of the ratio TPPTS/Pd(0) in the solution, even during catalysis. Indeed, under some conditions, the allylation reaction of 4 liberates TPPTS, which will be in equilibrium with the unreacted complex. The chemical shift value of 4 will then allow an estimation of the TPPTS/complex ratio in the solution
    • With a Pd concentration of 0.011 M, the following values were obtained: n (TPPTS/Pd(0) ratio) = 3, δ 23.85 ppm; n = 3.53, δ 21.75 ppm; n = 4.06, δ 17.97 ppm; n = 8, δ 2.06 ppm (TPPTS alone: δ-5 ppm). This variation allows an estimation of the ratio TPPTS/Pd(0) in the solution, even during catalysis. Indeed, under some conditions, the allylation reaction of 4 liberates TPPTS, which will be in equilibrium with the unreacted complex. The chemical shift value of 4 will then allow an estimation of the TPPTS/complex ratio in the solution.
  • 50
    • 33644798263 scopus 로고    scopus 로고
    • This result involves an equilibrium constant of dissociation K lower than 10-5. It is in agreement with recent results of the dissociation of Pd(TPP)3 (TPP, triphenylphosphine) into TPP and Pd(TPP)2. The dissociation constant was found to be 1.7 × 10-4 in organic medium: Amatore, C, Jutand, A, Mensah, L, Meyer, G, Fiaud, J, Legros, J. Eur. J. Org. Chem. 2006, 1185-1192
    • -4 in organic medium: Amatore, C.; Jutand, A.; Mensah, L.; Meyer, G.; Fiaud, J.; Legros, J. Eur. J. Org. Chem. 2006, 1185-1192.
  • 51
    • 52649129123 scopus 로고    scopus 로고
    • 4 catalyst: (a) Tsukahara, Y.; Kinoshita, H.; Inomata, K.; Kotake, H Bull. Chem. Soc. Jpn. 1984, 57, 3013-3014.
    • 4 catalyst: (a) Tsukahara, Y.; Kinoshita, H.; Inomata, K.; Kotake, H Bull. Chem. Soc. Jpn. 1984, 57, 3013-3014.
  • 53
    • 52649124688 scopus 로고    scopus 로고
    • More recently, alkenyl and alkyltriphenylphosphonium salts (RP +Ph3, X, were prepared from different metal-catalyzed additions of triphenylphosphine and strong acids to alkynes,33a, 1,3-alkadienes,33b and 1-alkenes. 33c Addition on alkynes with methanesulfonic acid with LiPF 6, X, PF6, catalyst Pd(TPP)4 or [RhCl(cod)]2: (a) Arisawa, M, Yamamuchi, M. J. Am. Chem. Soc. 2000, 122, 2387-2388. Addition on 1,3-alkadienes with trifluoromethanesulfonic acid, X, CF3SO3, catalyst RhH(TPP)4
    • 4:
  • 54
    • 0036012050 scopus 로고    scopus 로고
    • 3:
    • 3:
  • 58
    • 52649132239 scopus 로고    scopus 로고
    • When the ratio TPPTS/Pd was increased to 2.25 in the above preparation of 1a, the compounds 1a, 4, and 3a appeared in the molar ratio 1a/4/3a, 89/11/11, which showed that TPPTS in excess was partially allylated by la. 4 appeared at 23.26 ppm (normally at 23.85 ppm but TPPTS in excess made a shift of-0.59 ppm, A similar reaction in organic solvent was already observed with allylpalladium chloride dimer and triphenylphosphine (TPP, In the presence of more than 2 equiv of TPP in methanol, allyltriphenylphosphonium cation and palladium(0) TPP complex were formed. 36a An analogous reaction was observed in DMF without TPP excess because the palladium(O) complex was stabilized with chloride anion and one TPP molecule:36b (a) Shaw, B. L, Powel, J. J. Chem. Soc. A 1968, 774-777
    • 36b (a) Shaw, B. L.; Powel, J. J. Chem. Soc. A 1968, 774-777.
  • 66
    • 52649110516 scopus 로고    scopus 로고
    • 31P NMR spectrum: major signal, singlet at 27.73 ppm (90, other signals, two doublets at 27.03 ppm (10, d, JPP, 40 Hz) and 25.45 ppm (d, JPP, 40 Hz, probably the anti isomer [Pd(anti-C 4)L2, which should have signals similar to the signals of the complexes [Pd(C5)L2, Pd(C9)L2, and [Pd(C10)L 2, In the case of the preparation of [Pd(synC 4)L2, from the reaction of crotylpalladium chloride dimer with four TPPTS, the same spectrum was obtained
    • + from the reaction of crotylpalladium chloride dimer with four TPPTS, the same spectrum was obtained.
  • 68
    • 52649120154 scopus 로고    scopus 로고
    • With an excess of TPPTS 4 equiv of TPPTS/Pd, 6 equiv of HClO 4/Pd was added. Five equivalents of TPPTS/Pd was transformed into 3a
    • 4/Pd was added. Five equivalents of TPPTS/Pd was transformed into 3a.
  • 69
    • 52649125550 scopus 로고    scopus 로고
    • Or at pH 3 and 9 with allyl alcohol (pH influence study).
    • Or at pH 3 and 9 with allyl alcohol (pH influence study).
  • 70
    • 52649173644 scopus 로고    scopus 로고
    • Geraniol and prenol reactions were slow at pH 7. The reactions were faster at pH 6 and 5. Total conversions were obtained at pH 4.5.
    • Geraniol and prenol reactions were slow at pH 7. The reactions were faster at pH 6 and 5. Total conversions were obtained at pH 4.5.
  • 71
    • 52649162243 scopus 로고    scopus 로고
    • With allyl alcohol (R, 10) without acid addition, the pH was increased and measured over 5.5 h. 31P NMR spectrum after 2 h 1a/4, 15, 3a/4,4, After 1 day, the pH of the solution was 11.65 and propylene was identified in the gas phase. The conversion of 4 was 100% into 1a. 3a had disappeared, but the amount of TPPTS oxide 2a present in the solution had increased 2a/1a, 2.20/1
    • 31P NMR spectrum after 2 h 1a/4, 15%; 3a/4,4%. After 1 day, the pH of the solution was 11.65 and propylene was identified in the gas phase. The conversion of 4 was 100% into 1a. 3a had disappeared, but the amount of TPPTS oxide 2a present in the solution had increased (2a/1a = 2.20/1).
  • 72
    • 52649105289 scopus 로고    scopus 로고
    • 31P NMR peaks at 25.98, 25.61 ppm (major) and 25.22, 24.97 ppm. By addition of TPPDS to the allylation reaction of 4 by allyl alcohol (TPPDS/TPPTS = 1.6/3), an increase of signals due to TPPDS was actually observed. These peaks were also observed after the reaction of allylpalladium dimer and TPPTS.
    • 31P NMR peaks at 25.98, 25.61 ppm (major) and 25.22, 24.97 ppm. By addition of TPPDS to the allylation reaction of 4 by allyl alcohol (TPPDS/TPPTS = 1.6/3), an increase of signals due to TPPDS was actually observed. These peaks were also observed after the reaction of allylpalladium dimer and TPPTS.
  • 73
    • 52649156400 scopus 로고    scopus 로고
    • Homologous compounds with triphenylphosphine, 3a′-c′ and 2b′,c′, were already synthesized with available H NMR analysis (except 2c′, 3a′, allyltriphenylphosphonium chloride, was synthesized from the TPP reaction with allyl chloride,47a 3b′, 2-propenyltriphenylphosphonium bromide, from 3a′ bromide (prepared from TPP and allyl bromide) isomerization in a refluxing 2-methoxyethanol solution,47b 3c′, 2-hydoxypropyltriphenylphosphonium hydroxide, from TPP reaction with propylene oxide,47c 3c′ iodide, from TPP reaction with propylene oxide, NaI, and carbon dioxide,47d (d, 2b′, propenyldiphenylphosphine oxide, from (C6H 5)2POCl and 1-bromopropene Grignard reagent,47e and 2c′, 2-hydoxypropyldiphenylphosphine oxide, from (C6H 5)2HPO reaction with propylene carbonate:47f (a) Buchi, G
    • 47f (a) Buchi, G.; Wüest, H, Helv. Chim. Acta 1971, 188-189, 1681-1687.
  • 76
    • 0041508224 scopus 로고    scopus 로고
    • (d) Huang, J.; Sin, M. J. Org. Chem. 2003, 68 (17), 6705-6709.
    • (2003) J. Org. Chem , vol.68 , Issue.17 , pp. 6705-6709
    • Huang, J.1    Sin, M.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.