Ligand effects in the rhodium catalysed reaction of butadiene and amines

Baker, Raymond; Halliday, D. E.

doi:10.1016/s0040-4039(01)84930-3

Cited by 28 publications

(4 citation statements)

References 11 publications

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“…One approach uses activated alkenes that can form π-benzyl or [M]-enolate intermediates ( Figure 1a ). 9 – 16 A second approach utilizes an allylic C–H activation followed by nucleophilic attack at the terminal carbon on the resulting π-allyl. 17 – 20 Alternatively, proximal Lewis basic groups can direct functionalization of the alkene to afford the favored metallacycle ( Figure 1b ).…”

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confidence: 99%

Palladium-catalysed anti-Markovnikov selective oxidative amination

et al. 2018

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In recent years the synthesis of amines and other nitrogen containing motifs has been a major area of research in organic chemistry due to their being widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a Pd-catalyzed oxidative amination reaction, where the addition of the nitrogen occurs at the less substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide via trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favored products. Both the scope of the transformation and mechanistic investigations are reported.

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confidence: 99%

Palladium-catalysed anti-Markovnikov selective oxidative amination

et al. 2018

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“…Addition of amines yields unsaturated alkyl amines. The reaction can be catalyzed by homogeneous catalysts such as Rh[P(C 6 H 5 ) 3 ] 3 Cl (41) or heterogeneous catalysts such as MgO and other solid bases (42).…”

Section: Reactionsmentioning

confidence: 99%

Butadiene

Sun

Wristers

2002

Kirk-Othmer Encyclopedia of Chemical Technology

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Butadiene, C 4 H 6 , exists in two isomeric forms: 1,3‐butadiene and 1,2‐butadiene. 1,3‐Butadiene is a commodity product of the petrochemical industry. Elastomers consume the bulk of 1,3‐butadiene, led by the manufacture of styrene–butadiene rubber (SBR). 1,3‐Butadiene is manufactured primarily as a coproduct of steam cracking to produce ethylene in the United States, Western Europe, and Japan. However, in certain parts of the world it is still produced from ethanol. The other isomer, 1,2‐butadiene, has no significant current commercial interests. 1,3‐Butadiene is a noncorrosive, colorless, flammable gas at room temperature and atmospheric pressure. It has a mildly aromatic odor. It is sparingly soluble in water, slightly soluble in methanol and ethanol, and soluble in organic solvents like diethyl ether, benzene, and carbon tetrachloride. The conjugated double bonds of 1,3‐butadiene allow a large number of reactions at both the 1,2‐ and 1,4‐positions. These reactions include addition, hydrogenation, oxidation, Diels–Alder, oligomerization, and polymerization reactions. Many of these reactions produce large volumes of important industrial materials. Butadiene reacts with a large number of chemicals, has an inherent tendency to dimerize and polymerize, and is toxic. Therefore, specific handling, storage, and shipping procedures must be followed. U.S. shipments of butadiene, which is classified as a flammable compressed gas, are regulated by the Department of Transportation. Short‐term exposure to high concentrations of butadiene may cause irritation to the eyes, nose, and throat. Dermatitis and frostbite may result from exposure to the liquid and the evaporating gas. In several epidemiological studies, elevation in mortality was observed for small subgroups and tumor types. Updated exposure limits are given. Butadiene is used primarly in polymers. Other uses are given.

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“…Thus morpholine adds to 1,3-butadiene in the presence of RhCl 3 .3H 2 O to give a mixture of 1,2-(Markovnikov) and 1,4-hydroamination products in good overall yield (Eq. 4.42) [171,172].…”

Section: Activation Of the Dienementioning

confidence: 99%