{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,17]],"date-time":"2025-10-17T13:28:31Z","timestamp":1760707711208},"reference-count":60,"publisher":"Wiley","issue":"38","license":[{"start":{"date-parts":[[2006,8,23]],"date-time":"2006-08-23T00:00:00Z","timestamp":1156291200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2006,9,25]]},"DOI":"10.1002\/anie.200600447","type":"journal-article","created":{"date-parts":[[2006,8,23]],"date-time":"2006-08-23T10:51:23Z","timestamp":1156330283000},"page":"6386-6391","source":"Crossref","is-referenced-by-count":80,"title":["High\u2010Yield Ruthenium\u2010Catalyzed Friedel\u2013Crafts\u2010Type Allylation Reactions Using Dicationic Ru<sup>IV<\/sup> Catalysts"],"prefix":"10.1002","volume":"45","author":[{"given":"Ignacio","family":"Fern\u00e1ndez","sequence":"first","affiliation":[]},{"given":"Ren\u00e9","family":"Hermatschweiler","sequence":"additional","affiliation":[]},{"given":"Frank","family":"Breher","sequence":"additional","affiliation":[]},{"given":"Paul S.","family":"Pregosin","sequence":"additional","affiliation":[]},{"given":"Luis F.","family":"Veiros","sequence":"additional","affiliation":[]},{"given":"Maria Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2006,9,19]]},"reference":[{"key":"e_1_2_2_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0506410"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja043097o"},{"key":"e_1_2_2_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500136"},{"key":"e_1_2_2_2_4","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500136"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja050770g"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2004.11.017"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090334"},{"key":"e_1_2_2_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199702881"},{"key":"e_1_2_2_6_2","unstructured":"\u00a0"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00146a041"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo960997h"},{"key":"e_1_2_2_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971090333"},{"key":"e_1_2_2_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199702851"},{"key":"e_1_2_2_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.05.124"},{"key":"e_1_2_2_10_3","doi-asserted-by":"publisher","DOI":"10.1021\/ma0501287"},{"key":"e_1_2_2_11_2","unstructured":"\u00a0"},{"key":"e_1_2_2_12_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-49348-5_1"},{"key":"e_1_2_2_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2003.12.006"},{"key":"e_1_2_2_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200404219"},{"key":"e_1_2_2_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/3527603832"},{"key":"e_1_2_2_15_2","unstructured":"\u00a0"},{"key":"e_1_2_2_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020315)114:6<1101::AID-ANGE1101>3.0.CO;2-2"},{"key":"e_1_2_2_16_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020315)41:6<1059::AID-ANIE1059>3.0.CO;2-5"},{"key":"e_1_2_2_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020027w"},{"key":"e_1_2_2_18_2","unstructured":"\u00a0"},{"key":"e_1_2_2_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200352257"},{"key":"e_1_2_2_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200352257"},{"key":"e_1_2_2_20_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2003-37120"},{"key":"e_1_2_2_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/b406039c"},{"key":"e_1_2_2_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200404023"},{"key":"e_1_2_2_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2005.11.051"},{"key":"e_1_2_2_24_2","unstructured":"\u00a0"},{"key":"e_1_2_2_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049057a"},{"key":"e_1_2_2_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200500967"},{"key":"e_1_2_2_26_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200500967"},{"key":"e_1_2_2_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/om050749o"},{"key":"e_1_2_2_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/om051050l"},{"key":"e_1_2_2_29_2","unstructured":"\u00a0"},{"key":"e_1_2_2_30_2","unstructured":"Synthesis of3: AgPF6(48 mg 0.174 mmol) was added to a solution of [Ru(Cp*)Cl(CH3CN)(\u03b73\u2010PhCHCHCH2)]PF6(100 mg 0.174 mmol) in a mixture of toluene and acetonitrile (2 mL:2 mL). The reaction mixture was stirred for 16 h after which time the solution was filtered and then slowly concentrated under vacuum. The resulting crude solid was washed with diethyl ether to afford an oil which was dissolved in dichloromethane filtered and dried under vacuum to afford a brown\u2010yellow solid. This solid was dissolved in dichloromethane filtered and dried under vacuum. This sequence was repeated one more time. Yield: 78\u2009% (98 mg). An acetone solution of this solid was layered withn\u2010pentane and stored at 5\u2009\u00b0C to afford air\u2010sensitive crystals of3 which were suitable for X\u2010ray diffraction.1H NMR ([D6]acetone 298 K 400.13 MHz):\u03b4=1.96 (s 15\u2009H) 2.37 (s 3\u2009H) 2.68 (s 3\u2009H) 3.41 (d 1\u2009H J=10.4 Hz) 4.87 (d 1\u2009H J=6.4 Hz) 5.31 (d 1\u2009H J=12.0 Hz) 6.59 (ddd 1\u2009H J=12.0 10.4 6.4 Hz) 7.58 (m 2\u2009H J=7.6 7.2 Hz) 7.74 (m 2\u2009H J=7.6 1.4 Hz) 7.90\u2002ppm (m 2\u2009H J=7.2 Hz);13C NMR:\u03b4=3.7 (CH3) 4.0 (CH3) 9.2 (CH3) 66.3 (H2Callyl) 108.8 (C) 94.1 (HCallyl) 103.3 (HCallyl) 129.1 (Cnitrile) 129.2 (Cnitrile) 129.9 (HCAr) 131.1 (HCAr) 132.6 (HCAr) 133.6 ppm (Cipso). Elemental analysis (%) calcd for C23H30F12N2P2Ru: C 38.08 H 4.17 N 3.86; found: C 38.46 H 4.38 N 3.20; ESI\u2010MS:m\/z: 436.1 [M+] 354.1 [M+\u22122\u2009CH3CN] 237.0 [M+\u22122\u2009CH3CN\u2212PhCHCHCH2). Synthesis of4: AgPF6(48 mg 0.174 mmol) was added to a solution of [Ru(Cp*)Cl(CH3CN)(\u03b73\u2010PhCHCHCH2)]PF6(100 mg 0.174 mmol) in DMF (2 mL). The reaction mixture was stirred for 16 h after which time the solution was filtered and then slowly concentrated under vacuum. The resulting crude mixture was washed with diethyl ether. The resulting red oil was dissolved in dichloromethane filtered and dried under vacuum to afford a red\u2010purple solid. This solid was dissolved in dichloromethane filtered and dried under vacuum. This sequence was repeated one more time. Yield: 84\u2009% (115 mg). A dichloromethane solution of this solid was then layered withn\u2010pentane and stored at \u221230\u2009\u00b0C to afford red air\u2010sensitive crystals of4 which were suitable for X\u2010ray diffraction.1H NMR ([D6]acetone 298 K 400.13 MHz):\u03b4=1.76 (s 15\u2009H) 2.60 (d 3\u2009H J=1.0 Hz) 3.05 (s 3\u2009H) 3.13 (d 3\u2009H J=1.0 Hz) 3.28 (s 3\u2009H) 3.64 (dd 1\u2009H J=10.0 0.9 Hz) 4.70 (dd 1\u2009H J=6.5 0.9 Hz) 5.49 (d 1\u2009H J=11.0 Hz) 6.48 (ddd 1\u2009H J=11.0 10.0 6.5 Hz) 7.12 (s 1\u2009H) 7.50 (m 2\u2009H J=7.8 7.5 Hz) 7.72 (m 1\u2009H J=7.8 1.5 Hz) 7.75 (m 2\u2009H J=7.5 Hz) 7.95 ppm (s 1\u2009H);13C NMR:\u03b4=8.9 (CH3) 33.2 (CH3) 33.8 (CH3) 39.2 (CH3) 39.4 (CH3) 66.0 (H2Callyl) 107.9 (C) 96.9 (HCallyl) 98.4 (HCallyl) 129.9 (HCAr) 131.5 (HCAr) 131.6 (HCAr) 134.0 (Cipso) 166.5 (Cdmf) 167.8 ppm (Cdmf); ESI\u2010MS:m\/z: 459.1 [M+\u2212Me2NCHO+MeOH) 427.1 [M+\u2212Me2NCHO] 354.1 [M+\u22122\u2009Me2NCHO]. Catalysis: In a typical experiment the Ru catalyst precursor3or4(0.002 mmol 3 mol\u2009%) was added to a mixture consisting of acetonitrile (0.5 mL) and the allylic carbonate substrate (0.07 mmol) in an oven\u2010dried 5\u2010mm NMR tube. The arene derivative (0.21 mmol) was added and the mixture was monitored by1H NMR spectroscopy at 353 K. Crystal structure of3: Yellow crystals of [Ru(Cp*)(\u03b73\u2010CH2CHCHPh)(MeCN)2](PF6)2\u22c5acetone were obtained from an acetone solution of3which was layered withn\u2010hexane; C26H36F12N2OP2Ru triclinic space groupP$\\bar 1$;a=9.535(1) b=11.750(1) c=15.879(1) \u00c5 \u03b1=109.395(1) \u03b2=96.719(1) \u03b3=100.965(1)\u00b0 V=1615.8(2) \u00c53 Z=2 \u03c1calcd=1.611 Mg\u2009m\u22123 crystal dimensions 0.48\u00d70.27\u00d70.23 mm Bruker SMART Apex diffractometer with CCD detector MoK\u03b1radiation (0.71073 \u00c5) 200 K 2\u0398max=56.68\u00b0 16\u2009798 reflections 7984 independent (Rint=0.0217) empirical absorption correction SADABS (ver. 2.03) direct methods refinement against full matrix (versusF2) with SHELXTL (ver. 6.12) and SHELXL\u201097 406 parameters R1=0.0504 and wR2 (all data)=0.1363 max.\/min. residual electron density 1.106\/\u22120.464 e\u2009\u00c5\u22123. All non\u2010hydrogen atoms were refined anisotropically; the contribution of the hydrogen atoms in their calculated positions was included in the refinement using a riding model. Crystal structure of4: Red crystals of [Ru(Cp*)(\u03b73\u2010CH2CHCHPh)(dmf)2](PF6)2\u22c5CH2Cl2\u22c5alkane were obtained from a methylene chloride solution which was layered withn\u2010hexane; C28H40Cl2F12N2O2P2Ru orthorhombic space groupPccn;a=21.369(1) b=22.712(1) c=15.580(1) \u00c5 V=7561.4(6) \u00c53 Z=8 \u03c1calcd=1.579 Mg\u2009m\u22123 crystal dimensions 0.44\u00d70.42\u00d70.32 mm Bruker CCD1k diffractometer MoK\u03b1radiation (0.71073 \u00c5) 200 K 2\u03b8max=52.74\u00b0 58\u2009019 reflections 7735 independent (Rint=0.0272) empirical absorption correction SADABS (ver. 2.03) direct methods refinement against full matrix (versusF2) with SHELXTL (ver. 6.12) and SHELXL\u201097 515 parameters R1=0.0457 and wR2 (all data)=0.1558 max.\/min. residual electron density 1.193\/\u22120.568 e\u2009\u00c5\u22123. All non\u2010hydrogen atoms were refined anisotropically; the contribution of the hydrogen atoms in their calculated positions was included in the refinement using a riding model. One CH2Cl2molecule could be refined. Presumably owing to solvent loss or incomplete incorporation additional crystal solvent molecule(s) could only be refined by positioning two carbon atoms (\u00d70.5\u2009C4) one of which had to be split over two positions and refined using the ISOR restraint. One of the PF6\u2212anions was disordered. Each of the fluorine atoms was split over two positions which were refined against each other (FVAR=0.53). CCDC\u2010 295048 and 295049 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_2_31_2","unstructured":"A reviewer has correctly suggested that the Friedel\u2013Crafts chemistry might arise from a rearrangement of the branched organic product PhCH(OPh)CHCH2formed from the nucleophilic attack of phenol on the RuIVallyl complex. To test this we allowed this product PhCH(OPh)CHCH2 to react with catalyst3under our standard conditions (CH3CN at 353 K). After 12 h that is more than one order of magnitude longer than necessary for 100\u2009% conversion we did find about 60\u2009% of the Friedel\u2013Crafts product. However this reaction is much too slow to be relevant."},{"key":"e_1_2_2_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo010438x"},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol0069251"},{"key":"e_1_2_2_34_2","unstructured":"\u00a0"},{"key":"e_1_2_2_35_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1997.137"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo982178y"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0506004"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200301679"},{"key":"e_1_2_2_38_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200301679"},{"key":"e_1_2_2_39_2","unstructured":"\u00a0"},{"key":"e_1_2_2_40_2","doi-asserted-by":"publisher","DOI":"10.1039\/a701115f"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049358k"},{"key":"e_1_2_2_42_2","unstructured":"DFT calculations were performed with the Gaussian\u200998 software package using the mPW1PW91 hybrid functional. The basis set that was used included a standard SDD which was augmented with anf\u2010polarization function for Ru and 4\u201031G(d) for the other atoms. The atomic charges resulted from a natural population analysis (NPA). Computational details and the corresponding list of references are given asSupporting Information."},{"key":"e_1_2_2_43_2","unstructured":"\u00a0"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1002\/1522-2675(20011017)84:10<2833::AID-HLCA2833>3.0.CO;2-O"},{"key":"e_1_2_2_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/B305046G"},{"key":"e_1_2_2_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr0406716"},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049248d"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1039\/b415560b"},{"key":"e_1_2_2_49_2","unstructured":"The radii from the X\u2010ray data for the cations in3 4 and5are 4.6 4.8 and 4.5 \u00c5 respectively."},{"key":"e_1_2_2_50_2","unstructured":"In a typical catalytic experiment the concentration of the catalyst precursor is 4.2 mM. The PGSE diffusion studies were performed at 2 mM so that in the catalytic solution even more aggregation is expected."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.200600447","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.200600447","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,16]],"date-time":"2023-10-16T08:42:50Z","timestamp":1697445770000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.200600447"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2006,9,19]]},"references-count":60,"journal-issue":{"issue":"38","published-print":{"date-parts":[[2006,9,25]]}},"alternative-id":["10.1002\/anie.200600447"],"URL":"https:\/\/doi.org\/10.1002\/anie.200600447","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2006,9,19]]}}}