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The acetato\u2010bridged structure was supported by the ESI mass spectrum of the palladium complex1(see Supporting Information)."},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic049744u"},{"key":"e_1_2_2_34_2","unstructured":"Cycloadduct3\u2009awas also contaminated with 5\u2009% of an unidentified byproduct."},{"key":"e_1_2_2_35_2","unstructured":"\u00a0"},{"key":"e_1_2_2_36_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1997.1273"},{"key":"e_1_2_2_37_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.72.2475"},{"key":"e_1_2_2_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9942890"},{"key":"e_1_2_2_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr000666b"},{"key":"e_1_2_2_40_2","volume-title":"Ruthenium Catalysts and Fine Chemistry","year":"2004"},{"key":"e_1_2_2_41_2","doi-asserted-by":"publisher","DOI":"10.1002\/3527603832.ch4"},{"key":"e_1_2_2_42_2","unstructured":"\u00a0"},{"key":"e_1_2_2_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00017a046"},{"key":"e_1_2_2_44_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(98)00022-2"},{"key":"e_1_2_2_45_2","unstructured":"Other catalysts associated with two PPh3ligands such as [PdCl{\u03b73\u2010(C3H5)}2] Pd(OAc)2 and [Pd2(dba)3]\u22c5CHCl3(dba=dibenzylideneacetone) did not promote the reaction at all."},{"key":"e_1_2_2_46_2","unstructured":"Toluene gave the best results. The [2+1] cycloaddition proceeded well in heterogeneous media in solvents such as Et2O (74\u2009% yield) THF (59\u2009% yield) or CH2Cl2(49\u2009% yield). The lowest yields were obtained with more polar solvents such asN N\u2010dimethylformamide (10\u2009% yield) or CH3CN (6\u2009% yield)."},{"key":"e_1_2_2_47_2","unstructured":"The catalytic system was stable under the experimental conditions described and could be recovered after the reaction by column chromatography."},{"key":"e_1_2_2_48_2","unstructured":"A difference in reactivity was observed by using trimethylsilylacetylene in place of propargylsilane3\u2009c: Only an adduct of hydroalkynylation was obtained as a single diastereomer in 68\u2009% yield."},{"key":"e_1_2_2_49_2","doi-asserted-by":"crossref","first-page":"543","DOI":"10.1002\/0470021209.ch6","volume-title":"Palladium Reagents and Catalysts: New Perspectives for the 21st Century","author":"Tsuji J.","year":"2004"},{"key":"e_1_2_2_49_3","doi-asserted-by":"publisher","DOI":"10.1002\/0470021209.ch7"},{"key":"e_1_2_2_50_2","unstructured":"\u00a0"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00443a038"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00876a012"},{"key":"e_1_2_2_53_2","unstructured":"These rearrangments are geometrically constrained to occur by a \u03c32s+\u03c32\u03c0 mechanism which is a symmetry\u2010forbidden reaction. They have therefore been generally interpreted to occur by cleavage to a diradical followed by rapid intramolecular trapping of the diradical by the \u03c0 bond (see reference [21a])."},{"key":"e_1_2_2_54_2","unstructured":"The structure and stereochemistry of compounds4\u2009iand6\u2009iwere confirmed by X\u2010ray analysis (see reference [36])."},{"key":"e_1_2_2_55_2","unstructured":"The same reaction carried out with cyclopentene in place of norbornene derivatives did not work. No oligomers or self\u2010coupling adducts of the phenylethyne3\u2009ahave been observed."},{"key":"e_1_2_2_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00109a015"},{"key":"e_1_2_2_57_2","unstructured":"\u00a0"},{"key":"e_1_2_2_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0690(200005)2000:9<1799::AID-EJOC1799>3.0.CO;2-B"},{"key":"e_1_2_2_59_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0690(200103)2001:5<1009::AID-EJOC1009>3.0.CO;2-3"},{"key":"e_1_2_2_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9624937"},{"key":"e_1_2_2_61_2","unstructured":"\u00a0"},{"key":"e_1_2_2_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar980016i"},{"key":"e_1_2_2_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr00002a005"},{"key":"e_1_2_2_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-0682(199907)1999:7<1057::AID-EJIC1057>3.0.CO;2-9"},{"key":"e_1_2_2_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/om000834q"},{"key":"e_1_2_2_66_2","unstructured":"There are two possible mechanisms for the formation of Pd vinylidene complexesBfrom \u03b72\u2010coordinated alkyne intermediateA. The first involves a direct 1 2\u2010hydrogen migration over the carbon triple bond. In contrast the second mechanism occurs through a 1 3\u2010shift of the hydride to the alkynyl ligand after oxidative addition of the C\uf8ffH bond to Pd."},{"key":"e_1_2_2_67_2","unstructured":"The position of the deuterium was based on the disappearance of the signal of C\u2010H at\u03b4=6.55 ppm (see Supporting Information)."},{"key":"e_1_2_2_68_2","unstructured":"For recent reviews see:"},{"key":"e_1_2_2_69_2","first-page":"903","author":"H","year":"1997","journal-title":"Chem. Commun."},{"key":"e_1_2_2_70_2","first-page":"178","author":"Touchard D.","year":"1998","journal-title":"Coord. Chem. Rev."},{"key":"e_1_2_2_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200103)2001:3<571::AID-EJIC571>3.0.CO;2-2"},{"key":"e_1_2_2_72_2","unstructured":"Pure enantiomers were obtained by semipreparative chiral HPLC on chiralpak AD or AS (250\u00d710 mm2) columns using hexane\/ethanol (90:10) or ethanol as eluents. ForL\u20092 the absolute configuration at phosphorus is currently unknown."},{"key":"e_1_2_2_73_2","unstructured":"\u00a0"},{"key":"e_1_2_2_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01358a028"},{"key":"e_1_2_2_75_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00974a045"},{"key":"e_1_2_2_76_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19820940805"},{"key":"e_1_2_2_76_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198205671"},{"key":"e_1_2_2_77_2","first-page":"1155","volume-title":"Stereochemistry of Organic Compounds","year":"1994"},{"key":"e_1_2_2_78_2","unstructured":"Alkylidenecyclopropanes have served as useful building blocks in organic synthesis. 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