TY - JOUR
T1 - Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes
AU - Itazaki, Masumi
AU - Nishihara, Yasushi
AU - Takimoto, Hisami
AU - Yoda, Chikako
AU - Osakada, Kohtaro
N1 - Funding Information:
This work was partially supported by a Grant-in-aid for Scientific Research for Young Chemists No. 13740412 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
PY - 2005/11/1
Y1 - 2005/11/1
N2 - 2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.
AB - 2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.
KW - CC bond activation
KW - Diene
KW - Hydrido complex
KW - Methylenecyclopropane
KW - Rhodium
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U2 - 10.1016/j.molcata.2005.06.045
DO - 10.1016/j.molcata.2005.06.045
M3 - Article
AN - SCOPUS:25844524691
SN - 1381-1169
VL - 241
SP - 65
EP - 71
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
IS - 1-2
ER -