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Issue 43, 2010
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Regioselective functionalization of iminophosphoranes through Pd-mediated C–H bond activation: C–C and C–X bond formation

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Abstract

The orthopalladation of iminophosphoranes [R3P[double bond, length as m-dash]N–C10H7-1] (R3 = Ph31, p-Tol32, PhMe23, Ph2Me 4, N–C10H7-1 = 1-naphthyl) has been studied. It occurs regioselectively at the aryl ring bonded to the P atom in 1 and 2, giving endo-[Pd(μ-Cl)(C6H4-(PPh2[double bond, length as m-dash]N-1-C10H7)-2)-κ-C,N]2 (5) or endo-[Pd(μ-Cl)(C6H3-(P(p-Tol)2[double bond, length as m-dash]N–C10H7-1)-2-Me-5)-κ-C,N]2 (6), while in 3 the 1-naphthyl group is metallated instead, giving exo-[Pd(μ-Cl)(C10H6-(N[double bond, length as m-dash]PPhMe2)-8)-κ-C,N]2 (7). In the case of 4, orthopalladation at room temperature affords the kinetic exo isomer [Pd(μ-Cl)(C10H6-(N[double bond, length as m-dash]PPh2Me)-8)-κ-C,N]2 (11exo), while a mixture of 11exo and the thermodynamic endo isomer [Pd(μ-Cl)(C6H4-(PPhMe[double bond, length as m-dash]N–C10H7-1)-2)-κ-C,N]2 (11endo) is obtained in refluxing toluene. The heating in toluene of the acetate bridge dimer [Pd(μ-OAc)(C10H6-(N[double bond, length as m-dash]PPh2Me)-8)-κ-C,N]2 (13exo) promotes the facile transformation of the exo isomer into the endo isomer [Pd(μ-OAc)(C6H4-(PPhMe[double bond, length as m-dash]N–C10H7-1)-2)-κ-C,N]2 (13endo), confirming that the exo isomers are formed under kinetic control. Reactions of the orthometallated complexes have led to functionalized molecules. The stoichiometric reactions of the orthometallated complexes [Pd(μ-Cl)(C10H6-(N[double bond, length as m-dash]PPhMe2)-8)-κ-C,N]2 (7), [Pd(μ-Cl)(C6H4-(PPh2[double bond, length as m-dash]NPh)-2)]2 (17) and [Pd(μ-Cl)(C6H3-(C(O)N[double bond, length as m-dash]PPh3)-2-OMe-4)]2 (18) with I2 or with CO results in the synthesis of the ortho-halogenated compounds [PhMe2P[double bond, length as m-dash]N–C10H6–I-8] (19), [I–C6H4-(PPh2[double bond, length as m-dash]NPh)-2] (21) and [Ph3P[double bond, length as m-dash]NC(O)C6H3I-2-OMe-5] (23) or the heterocycles [C10H6-(N[double bond, length as m-dash]PPhMe2)-1-(C(O))-8]Cl (20), [C6H5-(N[double bond, length as m-dash]PPh2-C6H4–C(O)-2]ClO4 (22) and [C6H3-(C(O)-1,2-N–PPh3)-OMe-4]Cl (24).

Graphical abstract: Regioselective functionalization of iminophosphoranes through Pd-mediated C–H bond activation: C–C and C–X bond formation

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Supplementary files

Article information


Submitted
16 Feb 2010
Accepted
06 May 2010
First published
06 Oct 2010

Dalton Trans., 2010,39, 10422-10431
Article type
Paper

Regioselective functionalization of iminophosphoranes through Pd-mediated C–H bond activation: C–C and C–X bond formation

D. Aguilar, R. Navarro, T. Soler and E. P. Urriolabeitia, Dalton Trans., 2010, 39, 10422 DOI: 10.1039/C003241G

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