Synthesis of 7-Methyl- and 7-Phenylnorbornadiene

Nature of the Propagating Species in Ring-Opening Metathesis Polymerizations of Oxygen-Containing Monomers Using Well-Defined Ruthenium Initiators

“…All other solvents were used without prior purification. RuCl2(PCy3)2(dCHPh) 8 [1], 5-exo,6-endo-dicarbomethoxynorbornene 15 [4], 7-tert-butoxynorbornadiene 16 [5], exo,exo-N-phenyl-5,6-dicarboxyimidonorbornene 17 [6a], exo,exo-N-phenylmethyl-5,6-dicarboxyimidonorbornene 17 [6b], exo-5-methoxymethylnorbornene 18 [7], exo,exo-5,6-bis(methoxymethyl)norbornene 19 [8], 7-methylnorbornadiene 20 [9c], and endo,endo-5,6-bis(chloromethyl)norbornene 21,22 [12] were synthesized according to literature procedures. Norbornene [10] was dried over sodium and distilled under vacuum prior to use.…”

Novel Mode of C−C Bond Cleavage of Norbornadiene on a Dinuclear Ruthenium Complex

“…The latter mode of CÀC bond cleavage is observed in the protonation of [(h 5 -C 5 R 5 )Co(h 4 -norbornadiene)]. [6] To elucidate the reaction pathway to 3, complex 2 was allowed to react with 7-methylnorbornadiene [7] under similar conditions to those with norbornadiene. This reaction generated the analogous ruthenacycle [{(h 5 -C 5 Me 5 )Ru} 2 (mh 5 :h 1 :h 1 -C 5 H 3 CH 3 C 2 H 5 )(H)] (4) in which a methyl group was bound to C4 [Eq.…”

“…The first successful application of isolated diphenylzinc in this reaction was described by Fu and co-workers in 1997 who demonstrated that a chiral azaferrocene catalyzed its addition to 4-chlorobenzaldehyde affording the corresponding diarylmethanol with 57 % ee. [7] Soon after, Pu and co-workers [8] and Bolm and Mun Ä iz [9] independently developed other catalysts for the asymmetric phenylation of aldehydes based on 2,2'-dihydroxy-1,1'-biphenyl (BINOL) derivatives and planar-chiral ferrocenyl oxazoline 3, [10] respectively. Here we report on an improvement of the existing methodology which allows the catalytic synthesis of a wide range of arylphenylmethanols 2 from benzaldehydes 1 with very high enantioselectivities.…”

Novel Mode of C−C Bond Cleavage of Norbornadiene on a Dinuclear Ruthenium Complex

“…[6] To elucidate the reaction pathway to 3, complex 2 was allowed to react with 7-methylnorbornadiene [7] under similar conditions to those with norbornadiene. One involves C À C bond cleavage at C1 À C2 and C4 À C5 of norbornadiene.…”

“…The most prominent examples of the former are based on Coreys CBS reduction methodology [2] and Noyoris enantioselective ketone hydrogenation catalyzed by 2,2'bis(diphenylphosphanyl)-1,1'binaphthyl (BINAP)/diamine ruthenium complexes. [7] Soon after, Pu and co-workers [8] and Bolm and Mun Ä iz [9] independently developed other catalysts for the asymmetric phenylation of aldehydes based on 2,2'-dihydroxy-1,1'-biphenyl (BINOL) derivatives and planar-chiral ferrocenyl oxazoline 3, [10] respectively. Successful examples of the second strategy have only recently been described.…”