{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,26]],"date-time":"2025-10-26T20:55:18Z","timestamp":1761512118456},"reference-count":25,"publisher":"Wiley","issue":"28","license":[{"start":{"date-parts":[[2005,6,16]],"date-time":"2005-06-16T00:00:00Z","timestamp":1118880000000},"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":[[2005,7,11]]},"DOI":"10.1002\/anie.200500967","type":"journal-article","created":{"date-parts":[[2005,6,16]],"date-time":"2005-06-16T07:46:39Z","timestamp":1118907999000},"page":"4397-4400","source":"Crossref","is-referenced-by-count":73,"title":["Ruthenium\u2010Catalyzed Allylic Alkylation Reactions: Carbonate\u2010Based Catalysts and Intermediates"],"prefix":"10.1002","volume":"44","author":[{"given":"Ren\u00e9","family":"Hermatschweiler","sequence":"first","affiliation":[]},{"given":"Ignacio","family":"Fern\u00e1ndez","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":[[2005,7,4]]},"reference":[{"key":"e_1_2_2_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020027w"},{"key":"e_1_2_2_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr9409804"},{"key":"e_1_2_2_1_4","doi-asserted-by":"publisher","DOI":"10.1039\/a900861f"},{"key":"e_1_2_2_1_5","doi-asserted-by":"publisher","DOI":"10.1021\/cr030700x"},{"key":"e_1_2_2_1_6","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19931050410"},{"key":"e_1_2_2_1_7","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199305471"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja973298a"},{"key":"e_1_2_2_2_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja028497v"},{"key":"e_1_2_2_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(98)00142-7"},{"key":"e_1_2_2_3_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja980030q"},{"key":"e_1_2_2_4_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_4_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_4_4","doi-asserted-by":"publisher","DOI":"10.1021\/om020143p"},{"key":"e_1_2_2_4_5","doi-asserted-by":"publisher","DOI":"10.1016\/0022-328X(93)80158-8"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200352257"},{"key":"e_1_2_2_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200352257"},{"key":"e_1_2_2_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00004a055"},{"key":"e_1_2_2_6_3","doi-asserted-by":"publisher","DOI":"10.1039\/b002927k"},{"key":"e_1_2_2_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0102246"},{"key":"e_1_2_2_7_3","doi-asserted-by":"publisher","DOI":"10.1021\/om049616d"},{"key":"e_1_2_2_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/om049057a"},{"key":"e_1_2_2_9_2","unstructured":"Synthesis of3\u2009a. [RuCp*(CH3CN)3]PF6(64 mg 0.128 mmol) and4\u2009a(30 mg 0.128 mmol) were stirred in DMF (3 mL) for 30 min at room temperature. The solution volume was reduced in vacuum and diethyl ether was added precipitating an orange\u2010brown powder. The solid was washed with diethyl ether and dried under vacuum to yield 74 mg (94\u2009%) of the crude product.1H NMR (500 mHz [D7]DMF 298 K):\u03b4=1.53 (9\u2009H) 1.72 (15\u2009H) 3.52 (1\u2009H J=10 Hz) 4.66 (1\u2009H J=6.5 Hz) 5.11 (1\u2009H J=11.0 Hz) 6.36 (1\u2009H J=11.0 10.0 6.5 Hz) 7.42 (2\u2009H J=7.7 7.3 Hz) 7.62 (1\u2009H J=7.7 Hz) 7.74 ppm (2\u2009H J=7.3 Hz);13C NMR (126 mHz [D7]DMF 298 K):\u03b4=8.8 (CH3) 28.2 (CH3) 65.8 (H2Callyl) 85.9 (C) 90.2 (HCallyl) 99.9 (HCallyl) 107.2 (C) 129.2 (HCAr) 130.5 (HCAr) 130.8 (HCAr) 135.2 (Cipso) 164.4 ppm (CO3). Elemental analysis (%) calcd for C24H33O3F6PRu: C 46.83 H 5.40; found: C 46.15 H 5.25. ESI MS: 471.2 [M+] 427.2 [M+\u2212CO2] 371.2 353.2 [M+\u2212C5H9O3 M+\u2212C9H9]. Synthesis of3\u2009b. [RuCp*(CH3CN)3]PF6(55 mg 0.110 mmol) and4\u2009b(29 mg 0.110 mmol) were stirred in DMF (3 mL) for 30 min at room temperature. The solution volume was reduced in vacuum and diethyl ether was added precipitating an orange\u2010red powder. The solid was washed with diethyl ether and dried under vacuum to yield 67 mg (95\u2009%) of the crude product.1H NMR (500 mHz [D7]DMF 298 K):\u03b4=1.53 (9\u2009H) 1.70 (15\u2009H) 3.50 (1\u2009H J=9.6 Hz) 4.61 (1\u2009H J=6.4 Hz) 5.21 (1\u2009H J=11.1 Hz) 6.20 (1\u2009H J=11.1 9.6 6.4 Hz) 7.00 (2\u2009H J=8.6 Hz) 7.71 ppm (2\u2009H J=8.6 Hz);13C NMR(126 mHz [D7]DMF 298 K):\u03b4=8.8 (CH3) 28.3 (CH3) 55.7 (OCH3) 65.3 (H2Callyl) 85.7 (C) 93.2 (HCallyl) 98.6 (HCallyl) 106.3 (C) 114.8 (HCAr) 127.1 (Cipso) 132.8 (HCAr) 162.0 (Cipso) 164.3 ppm (CO3). Elemental analysis (%) calcd for C25H35O4F6PRu: C 46.51 H 5.46; found: C 46.31 H 5.40. ESI MS: 501.1 [M+] 457.2 [M+\u2212CO2] 401.1 383.1 [M+\u2212C5H9O3) 353.3 [M+\u2212C10H11O]. Catalysis: Dimethyl malonate (76 \u03bcL 0.65 mmol) and NaH (26 mg 0.64 mmol 60\u2009% dispersion in mineral oil) were stirred in DMF (1.5 mL) for 30 min at room temperature after which time the carbonate4\u2009aor5(0.21 mmol) and the catalyst1or3\u2009a(0.02 mmol 3 mol\u2009%) were added. The resulting solution was stirred at room temperature (see Table 1 for reaction times) and then diluted with diethyl ether and water (ca. 10 mL). After three extractions with diethyl ether the combined organic extracts were washed with water and brine dried over MgSO4 and concentrated. The crude product was purified by chromatography on silica gel (hexane\/ethyl acetate 6\/1). The branched\/linear ratio was determined by1H NMR spectroscopy."},{"key":"e_1_2_2_10_2","unstructured":"Crystal structure of3\u2009b: Orange single crystals were obtained from a CH2Cl2solution of3\u2009bwhich was layered withn\u2010pentane; C25H35F6O4PRu orthorhombic space groupPbca;a=11.030(1) b=21.378(2) c=23.626(2) \u00c5;V=5570.9(7) \u00c53;Z=8;\u03c1calcd=1.539 Mg\u2009m\u22123; crystal dimensions 0.58\u00d70.23\u00d70.13 mm; diffractometer Bruker SMART Apex; MoK\u03b1radiation 200 K 2\u0398max=49.42\u00b0; 41\u2009497 reflections 4749 independent (Rint=0.0451) direct methods; empirical absorption correction SADABS (v. 2.03); refinement against full matrix (versusF2) with SHELXTL (v. 6.12) and SHELXL\u201097 343 parameters R1=0.0596 and wR2 (all data)=0.1231 max.\/min. residual electron density 0.877\/\u22121.067 e\u2009\u00c5\u22123. The hydrogen atoms were placed in idealized positions and included as riding atoms. CCDC\u2010265478 (3\u2009b) contains 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_11_2","first-page":"356","volume-title":"Organometallics","year":"1992"},{"key":"e_1_2_2_12_2","unstructured":"DFT calculations were performed with the Gaussian 98 software package using the B3LYP hybrid functional. The basis set used for the geometry optimizations (VDZP) included a standard LanL2DZ augmented with a polarization function for Ru and 4\u201031G(d) for the other atoms. Single point energies were calculated for the optimized complexes using the same functional and a VTZP basis set: SDD with a polarization function for Ru and 6\u2010311G(d p) for the remaining elements. The atomic charges and Wiberg indices resulted from a Natural Population Analysis (NPA). Computational details and the corresponding list of references are given in the Supporting Information."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fanie.200500967","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.200500967","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,10,17]],"date-time":"2023-10-17T03:03:24Z","timestamp":1697511804000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.200500967"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2005,7,4]]},"references-count":25,"journal-issue":{"issue":"28","published-print":{"date-parts":[[2005,7,11]]}},"alternative-id":["10.1002\/anie.200500967"],"URL":"https:\/\/doi.org\/10.1002\/anie.200500967","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2005,7,4]]}}}