Synthesis of Heterocycles via Palladium π-Olefin and π-Alkyne Chemistry

Zeni, Gilson; Larock, Richard C.

doi:10.1021/cr020085h

Cited by 1,109 publications

(245 citation statements)

References 154 publications

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“…Alkynes are fundamental structural motifs and are versatile intermediates in chemical transformations [7][8][9][10][11] . Research towards the synthesis of alkynes has been pivotal throughout the history of organic chemistry.…”

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confidence: 99%

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Liu

2015

Nat Commun

137

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Methods to assemble alkynes are essential for synthesizing fine chemicals, pharmaceuticals and polymeric photo-/electronic materials. Using light as a clean energy form and water as a green solvent has the potential to make synthetic chemistry more environmentally friendly. Here we present a transition-metal-free coupling protocol between aryl alkyne and alkyl iodide enabled by photoenergy in water. Under ultraviolet irradiation and in basic aqueous media, aryl alkynes efficiently couple with a wide range of alkyl iodides including primary, secondary and tertiary ones under mild conditions. A tentative mechanism for the coupling is also proposed.

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confidence: 99%

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Liu

2015

Nat Commun

137

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“…0.1105 g (yield 91%) of complex 3a was obtained as yellow microcrystalline solid. (d,J ¼ 16.9,1H,SCH 2 ), 4.67 (d,J ¼ 16.9,1H,SCH 2 ),7.39 (dd,1H,J ¼ 7.7,5.1 Hz,7.51 (d,J ¼ 7.7 Hz,1H,7.86 (td,J ¼ 7.7,1.6 Hz,1H,9.38 (d,J ¼ 5.1 Hz,1H, PdS: C,33.09;H,3.07;N,2.03. Found: C,33.22;H,3.01;N,1.95.…”

Section: Synthesis Of Complex 3amentioning

confidence: 99%

“…(d,J ¼ 16.9,1H,SCH 2 ),7.34 (dd,1H,J ¼ 7.8,5.1 Hz,7.47 (d,J ¼ 7.8 Hz,1H,7.83 (td,J ¼ 7.7,1.7 Hz,1H,9.37 (d,J ¼ 5.1 Hz,1H, PdS: C,38.35;H,3.08;N,1.86. Found: C,38.44;H,3.12; N, 1.71.…”

Section: Synthesis Of Complex 3amentioning

confidence: 99%

Addition of halogens and interhalogens on palladacyclopentadienyl complexes stabilized by pyridyl−thioether N−S spectator ligands

Canovese

Visentin

Scattolin

et al. 2016

Journal of Organometallic Chemistry

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a b s t r a c tWe have studied from the experimental and theoretical point of view the oxidative addition of halogens (I 2 and Br 2 ) and interhalogens (ICl and IBr) on palladiumcyclopentadienyl complexes bearing heteroditopic pyridylÀthioether spectator ligands.Addition of I 2 or of a stoichiometric amount of Br 2 to a CDCl 3 solution of the starting palladacyclopentadienyl complexes yields the expected palladiumÀsÀbutadienyl derivatives. The bromide derivative in the presence of a further excess of Br 2 gives the wanted dibromoÀ(E, E)ÀsÀbutadienyl and the pyridylthioether palladium(II) dibromide species. The rates of these reactions have been determined.When the interhalogens are used as oxidizing agents the thermodynamically hampered species is formed at first. Only in the case of the reaction of IBr is the formation of the energetically hampered derivative followed by partial isomerization to the most stable complex. The rate of isomerization and the related equilibrium constant between isomers have been measured. On the basis of the experimental evidence and the computational approach we have proposed a plausible energetic path yielding the first formed unexpected species.Finally, the solid state structures of two reaction products were resolved and reported.

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“…Due to high electron density at position 3, indole undergoes electrophilic substitutions at position 2 and 3, respectively. A variety of synthetic methods for the indole ring system have been developed for the past hundred years [12][13][14][15] . The palladium-catalyzed annulation of 2-haloanilines with alkynes, in particular, is of great importance due to the easy availability of substrates 16 .…”

Section: Introductionmentioning

confidence: 99%

A Novel Synthesis of [4-(3-Methyl-1H-Indol-2-Yl)Phenyl]Phenylmethanone

Suhana¹,

Rȧjeswari²

2017

Orient. J. Chem

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We have developed a simple route for the synthesis of [4-(3-methyl-1H-indol-2-yl)phenyl](phenyl)methanone from easily available starting materials. The (4-propylphenyl) phenylmethanone was prepared by Friedel Craft's benzoylation of n-propyl benzene with benzoyl chloride in dichloromethane using aluminium chloride as the Lewis acid catalyst. Side chain bromination with N-bromo succinimide in tetra chloro methane furnished the bromo derivative which on oxidation with bis-tetra butyl ammonium dichromate gave 1, 4-diacyl benzene. The target molecule was obtained through Fischer indole cyclisation of the diacyl benzene namely 1-(4-benzoylphenyl)propan-1-one via the formation of the hydrazone, followed by cyclization in presence of boron trifluoride ethyl etherate in acetic acid. The structure of the target molecule was elucidated by IR, H 1 , C 13 NMR, Mass spectroscopy and elemental analysis. This method proves to be an efficient route for the synthesis of [4-(3-methyl-1H-indol-2-yl)phenyl](phenyl)methanone in high yields, thereby facilitating the generation of potential biologically active compounds.

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Synthesis of Heterocycles via Palladium π-Olefin and π-Alkyne Chemistry

Cited by 1,109 publications

References 154 publications

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Empowering a transition-metal-free coupling between alkyne and alkyl iodide with light in water

Addition of halogens and interhalogens on palladacyclopentadienyl complexes stabilized by pyridyl−thioether N−S spectator ligands

A Novel Synthesis of [4-(3-Methyl-1H-Indol-2-Yl)Phenyl]Phenylmethanone

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