TY - JOUR
T1 - Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds
AU - Choi, Jongwook
AU - Choliy, Yuriy
AU - Zhang, Xiawei
AU - Emge, Thomas J.
AU - Krogh-Jespersen, Karsten
AU - Goldman, Alan S.
PY - 2009/11/4
Y1 - 2009/11/4
N2 - (Chemical Equation Presented) (PCP)Ir (PCP = K3-C 6H3-2,6-[CH2P(t-Bu) 2]2) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH3)(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [kCH3OAr/kCD3OAr = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and ;-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by ß-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp 3)-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.
AB - (Chemical Equation Presented) (PCP)Ir (PCP = K3-C 6H3-2,6-[CH2P(t-Bu) 2]2) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH3)(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [kCH3OAr/kCD3OAr = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and ;-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by ß-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp 3)-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.
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U2 - 10.1021/ja906930u
DO - 10.1021/ja906930u
M3 - Article
C2 - 19827768
AN - SCOPUS:70350639427
VL - 131
SP - 15627
EP - 15629
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 43
ER -