Allylic alcohols as substrates for the palladium(0)-catalyzed allylic substitution

doi:10.1016/S0040-4039(00)60088-6

Tetrahedron Letters

Volume 34, Issue 1, 1 January 1993, Pages 179-182

https://doi.org/10.1016/S0040-4039(00)60088-6 Get rights and content

Abstract

A new method has been developed which allows palladium(0)-catalyzed allylic substitution to occur between allylic alcohols and anionic C-nucleophiles:

While allylic esters have frequently been used as substrates for the Pd(O)-catalyzed allylic substitution, the parent alcohols are much less reacti

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Citation Excerpt :
It was shown that the more acidic dicarbonyl compounds (pKa = 4.97–8.90) such as 42a,b were succeptible to the exclusive formation of bis allylationproducts 43, whereas the less acidic derivatives (pKa = 10.67–12.90), such as 42c-e, gave a mixture of bis and monoallylation derivatives 43 and 44, respectively (Scheme 18). In 1993, Kocovsky et al. described an alternative protocol for the 1,3-dicarbonyl compounds allylation involving a boron additive in which allylic alcohols are prior in situ activated before further reacting [68]. Indeed, primary and secondary allylic alcohols were reacted with BuLi to give the corresponding allylic alkoxide I, which is converted, by means of triphenyl boron (Ph3B), into the reactive species II that readily underwent a Pd(0)-catalyzed allylic substitution with only lithiodiethyl malonate as a typical C-nucleophile, leading to the allylation derivative III (Scheme 20).
The nucleophilic allylic substitutions have become one of the most powerful tools for the construction of carbon-carbon and carbon-heteroatom bonds in organic chemistry. This review focuses on the main previous reports dealing with the evolution of the direct nucleophilic substitutions of simple allylic alcohols or diversely functionalized ones (i.e., Morita-Baylis-Hillman alcohols) with 1,3-dicarbonyl compounds, under the catalysis of a variety of transition metals (Pd, Ir, Ru, Rh, Cu, Ni, Fe, Co, Au, Ag, Pt, W) and rare earth metals (Sc, La, Yb) complexes under activators-free conditions or in the presence of activators, as well as Lewis/Brønsted acids, and organocatalysts. In each synthetic process, a mechanistic aspect is proposed, along with a comparison of the observed regioselectivity in Pd-catalyzed allylic alkylations with that of other metals. Finally, numerous applications to the synthesis of complex molecules and natural products, are presented.
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A mild and efficient palladium‐catalyzed allylation reaction with allylic alcohols is described. The in situ activation of the allylic alcohol is achieved by using N,N‐dimethylacetamide dimethyl acetal and a simple palladium catalyst (i.e., Pd(PPh₃)₄). The reaction system does not require acid or base additives or specially designed ligands. In addition to carbon nucleophiles, nitrogen and oxygen nucleophiles can also be used with the allylic alcohol in this transformation.
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Nickel-based catalysis allows the efficient bis-allylation of soft nucleophiles with allylic alcohols. The reaction is best promoted by a combination of Ni(cod)₂ (cod = cyclooctadienyl) and diphenylphosphinobutane under additive-free conditions. Alternatively, nickel(II) precursors can be used provided that a reductant is used to generate the nickel(0) species. The NiCl₂/Zn combination is particularly simple, and can advantageously replace the use of the more air-sensitive Ni(cod)₂ precursor. The scope of the reaction was studied with nucleophiles and allylic derivatives suitable for bis-allylation reactions.
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Allylic alcohols as substrates for the palladium(0)-catalyzed allylic substitution

Abstract

J. Chem. Soc., Chem. Commun.

J. Org. Chem.

J. Chem. Soc., Chem. Commun.

Tetrahedron Lett.

J. Chem. Soc., Chem. Comm.

Tetrahedron Lett.

J. Am. Chem. Soc.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron

Acc. Chem. Res.

Angew. Chem. Int. Ed. Engl.

Pure Appl. Chem.

Acc. Chem. Res.

Synthesis

Acc. Chem. Res.

Pure Appl. Chem.

Angew. Chem. Int. Ed. Engl.

Tetrahedron: Asymmetry

Tetrahedron Lett.

J. Am. Chem. Soc.

Tetrahedron Lett.

J. Org. Chem.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

Tetrahedron Lett.

J. Am. Chem. Soc.