Reactions of cyclometalated palladium complexes with organolithium compounds or Grignard reagents. Selective Ortho alkylation and arylation of benzaldehydes, azobenzenes, and tertiary benzylic amines

Murahashi, Shun‐Ichi; Tamba, Yoshihiro; Yamamura, Masaaki; Yoshimura, N

doi:10.1021/jo00415a024

Cited by 65 publications

(19 citation statements)

References 23 publications

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“…The Murahashi cross-coupling is analogous to the Kumada-Corriu reaction but uses organolithium reagents as nucleophiles instead (Scheme 45). [211][212][213] Likewise, it has found only limited use in cross-coupling chemistry due to the high reactivity of the organolithium species. 214 Due to its excellent heat-and mass-transfer characteristics, microfluidics is ideally suited to perform extremely fast reactions in a controlled fashion (flash chemistry).…”

Section: Murahashi Cross-coupling Reactions In Flowmentioning

confidence: 99%

Cross-coupling in flow

2011

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Until recently, cross-coupling reactions have been exclusively performed in batch processes. With the advent of microfluidics, significant effort has been devoted to develop a wide variety of continuous-flow techniques to facilitate organic synthesis. In this critical review, we attempt to give an overview of the different continuous-flow methodologies that have been developed and utilized for cross-coupling reactions. In addition, we attempt to point out the advantages of continuous-flow when compared with their batch counterparts (246 references).

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Section: Murahashi Cross-coupling Reactions In Flowmentioning

confidence: 99%

Cross-coupling in flow

2011

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“…With Y-substituents such as 4'-or 5'-NO,, a side reaction occurs leading to [Pd (l),], 3. 3 4 We report here an extension of this chemistry in which we a ) change Reaction I so as to suppress the formation of 2 and obtain 4 selectively, b ) prepare a novel heterocyclic ketenimine from [PdCI (l)], and Bu'NrC, c) react cyclopalladated complexes with ethyl acrylate and I, thereby selectively synthesizing ortho -substituted aldehydes, d ) explore the organopalladium chemistry of our complexes with the acetylene CH,O,CC=CCO,CH, in MeOH, and e ) report the molecular structure of [Pd(OAc)(la)],.…”

Section: Reactions Of Cyclopalladated Benzylidene-anilinementioning

confidence: 99%

Reactions of Cyclopalladated Benzylidene‐aniline Schiff's Base Complexes. Selective Synthesis of 2′‐Substituted Schiff's Base Derivatives and the X‐Ray Crystal Structure of the Dimer [Pd(μ‐OAc)(5′‐OCH₃C₆H₃CHNC₆H₄‐4‐CH₃)]₂

Albinati

Pregosin

Rüedi

1985

Helvetica Chimica Acta

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The 2′‐cyclopalladated imine complex , reacts with CO in MeOH to afford the 2′‐substituted aryl imine 2′‐CO2CH3‐5′‐OCH3C6H3CHNTol (Tol = C6H4‐4‐CH3). The product of this reaction can be altered by changing the bridging ligand from AcO to Cl, in which case only the 5‐membered ring heterocyclic compound is obtained. [Pd(μ‐OAc)(1a)]2 with 2 equiv. of Ph3P and CO (1 atm) gives the heterocyclic which arises from two CO insertion reactions, whereas [PdX(1a)]2 (X = AcO, Cl) with 4 equiv. of CNBut and 4 equiv. of Ph2PCH2CH2PPh2 affords the heterocyclic ketenimine [PdCl(1a)]2 reacts with CH2CHCO2CH2CH3 to afford 2′(CHCHCO2CH2CH3)‐5′‐OCH3C6H3CHO, and [Pd(μ‐OAc)(1a)]2 with I2 to give 2′‐I‐5′‐OCH3C6H3CHO. Excess CH3O2CCCCO2CH3 reacts with various substituted cyclopalladated Schiff's bases in MeOH to afford which we formulate as possessing two PdC bonds, and one coordinated ester O atom. The X‐ray crystal structure of [Pd(μ‐OAc)(1a)]2 has been determined; relevant bond lengths [Å] and bond angles [°] are: PdO(1), 2.139(6), PdO(2), 2.026(6), PdN, 2.039(6), PdC(2′), 1.951(8), PdPd, 3.113(1), NPdC(2′), 80.9(3), NPdO(1), 97.5(2), C(2′)PdO(2), 91.7(3), O(1)PdO(2), 89.2(2).

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“…The alkaline-earth-metal dicyclopentadienyl compounds have been known for some time.1 While no quantitative structural information has been available for the heavier alkaline-earth metals strontium and barium,1 2 the lighter alkaline-earth-metal dicyclopentadienyls have been structurally characterized; bis(cyclopentadienyl)beryllium, Be(C5H5)2, has in the solid state one cyclopentadienyl ring ?) 5 6-bonded and the other ^-bonded to the beryllium atom. 3 In the gas phase the structure is similar, but due to the low scattering power of light atoms in the gas electron diffraction experiment, the bonding mode of the second cyclopentadienyl ring is uncertain, and a second investigation of the compound concludes that the second cyclopentadienyl ring is more or less t;3-bonded to the beryllium atom.4 Bis(cyclopentadienyl)magnesium or magnesocene, Mg(C5H5)2, has a monomeric, regular sandwich structure where the cyclopentadienyl rings are parallel and are T?5-bonded to the magnesium atom in both the gas and the crystalline phases.5,6 Bis(cyclopentadienyl)calcium, Ca-(C5H6)2, has a polymeric solid-state structure, with each calcium atom surrounded by four cyclopentadienyl rings in a fashion.7 This polymeric compound has a low vapor pressure, and attempts to obtain electron diffraction patterns of Ca(C5H5)2 for a determination of the molecular gas-phase structure have failed.…”

Section: Introductionmentioning

confidence: 99%

Molecular structures of alkaline earth-metal metallocenes: electron diffraction and ab initio investigations

Blom¹,

Fægri²,

Volden³

1990

Organometallics

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The thermal average molecular structures of Sr(C5Me5)2 and Ba(C5Me6)2 have been determined by gas electron diffraction. For both compounds the experimental data are consistent with molecular models where the C5Me5 rings are approximately ^-bonded to the metals and with ring centroid-metal-ring centroid angles close to 150°. The metal-carbon bond distances are ra(Sr-C) = 275.0 (8) pm and ra(Ba-C) = 289.8 (10) pm (mean values). The experimental results are compared to calculations on the model compounds Mg(C6H6)2 and Ca(C5H5)2 in a discussion of the bonding and structure of alkaline-earth-metal metallocenes.1085.

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Reactions of cyclometalated palladium complexes with organolithium compounds or Grignard reagents. Selective Ortho alkylation and arylation of benzaldehydes, azobenzenes, and tertiary benzylic amines

Cited by 65 publications

References 23 publications

Cross-coupling in flow

Cross-coupling in flow

Reactions of Cyclopalladated Benzylidene‐aniline Schiff's Base Complexes. Selective Synthesis of 2′‐Substituted Schiff's Base Derivatives and the X‐Ray Crystal Structure of the Dimer [Pd(μ‐OAc)(5′‐OCH₃C₆H₃CHNC₆H₄‐4‐CH₃)]₂

Molecular structures of alkaline earth-metal metallocenes: electron diffraction and ab initio investigations

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Reactions of cyclometalated palladium complexes with organolithium compounds or Grignard reagents. Selective Ortho alkylation and arylation of benzaldehydes, azobenzenes, and tertiary benzylic amines

Cited by 65 publications

References 23 publications

Cross-coupling in flow

Cross-coupling in flow

Reactions of Cyclopalladated Benzylidene‐aniline Schiff's Base Complexes. Selective Synthesis of 2′‐Substituted Schiff's Base Derivatives and the X‐Ray Crystal Structure of the Dimer [Pd(μ‐OAc)(5′‐OCH3C6H3CHNC6H4‐4‐CH3)]2

Molecular structures of alkaline earth-metal metallocenes: electron diffraction and ab initio investigations

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Reactions of Cyclopalladated Benzylidene‐aniline Schiff's Base Complexes. Selective Synthesis of 2′‐Substituted Schiff's Base Derivatives and the X‐Ray Crystal Structure of the Dimer [Pd(μ‐OAc)(5′‐OCH₃C₆H₃CHNC₆H₄‐4‐CH₃)]₂