25893-85-0Relevant articles and documents
Alkyne competition in the benzannulation reaction with chromium carbene complexes
Wu, Chunrui,Berbasov, Dmytro O.,Wulff, William D.
experimental part, p. 4441 - 4452 (2010/10/02)
(Figure presented) The benzannulation reaction of Fischer carbene complexes is investigated under conditions where the reaction of the carbene complex is occurring in the presence of two different alkynes. A series of competition experiments are examined where the effects of various structural factors are explored by pitting 10 different carbene complexes with 11 different alkynes. Terminal alkynes will react selectively over internal alkynes in all cases examined including both aryl and alkenyl complexes. Aryl carbene complexes with methoxy substituents do not give quite as high selectivity for terminal alkynes over internal alkynes (～95:5) as do isopropoxy substituents (>99:1), whereas most alkenyl complexes give high selectivity with both substituents (>99:1). Competition experiments between two different terminal alkynes or between two different internal alkynes did not result in anything more than very modest selectivities at best (～2:1). Excellent selectivities were realized between two different terminal acetylenes if one of the terminal acetylene was protected with a trimethylsilyl group. Finally, it was demonstrated that the high selectivities between terminal and internal alkynes can be utilized in the reaction with molecules that contain both types of alkyne functions.
THE CHEMISTRY OF η5-CpCo(CO)(maleoyl) AND η5-CpCo(CO)(phthaloyl) COMPLEXES
Liebeskind, Lanny S.,Jewell, Charles F. Jr.
, p. 305 - 320 (2007/10/02)
Insertion of η5-CpCo(CO)2 into dimethylcyclobutenedione and benzocyclobutenedione gave high yields of η5-CpCo(CO)(dimethylmaleoyl) and η5-CpCo(CO)(phthaloyl); respectively.Replacement of the carbon monoxide ligand in these complexes with thermally labile ligands (CH3CN, PhCN, C5H5N, (C2H5)2S) allowed a facile reaction with alkynes to occur.The maleoyl cobalt complex gave very high yields of stable η5-CpCo(CO)(benzoquinone) complexes which cleaved to the free quinones on treatment with cerium(IV).The phthaloylcobalt complex reacted to form unstable η5-CpCo(CO)(naphthoquinone) complexes and free naphthoquinones.
