Ruthenium‐Catalyzed Synthesis of Allylic Alcohols: Boronic Acid as a Hydroxide Source

Bouziane, Asmae; Hélou, Marion; Carboni, Bertrand; Carreaux, François; Demerseman, Bernard; Bruneau, Christian; Renaud, Jean‐Luc

doi:10.1002/chem.200702030

Cited by 53 publications

(24 citation statements)

References 78 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…13 C NMR (100 MHz, CDCl 3 ): δ = 166.8, 149.2, 142.6, 136.4, 134.0, 130.2, 124.4, 122.8, 121.4, 59.6, 14.6. The 1 H and 13 C spectra were found to be in agreement with Bouziane et al 41…”

Section: Methodssupporting

confidence: 88%

Exploration of amino‐functionalized ionic liquids as ligand and base for Heck reaction

Liu

Wang

2010

Applied Organom Chemis

View full text Add to dashboard Cite

A kind of amino-functionalized ionic liquid has been prepared and investigated as ligand and base for the Heck reactions between aryl iodides and bromides with olefins in the presence of a catalytic amount of Pd submicron powder in [Bmim]PF 6 . The reactions generated the corresponding products in excellent yields under mild reaction conditions. The generality of this catalytic system to the different substrates also gave satisfactory results. The key feature of the reaction is that Pd species and ionic liquids were easily recovered and reused six times with constant activity.

show abstract

“…13 C NMR (100 MHz, CDCl 3 ): δ = 166.8, 149.2, 142.6, 136.4, 134.0, 130.2, 124.4, 122.8, 121.4, 59.6, 14.6. The 1 H and 13 C spectra were found to be in agreement with Bouziane et al 41…”

Section: Methodssupporting

confidence: 88%

Exploration of amino‐functionalized ionic liquids as ligand and base for Heck reaction

Liu

Wang

2010

Applied Organom Chemis

View full text Add to dashboard Cite

show abstract

“…[7,8] In the reaction of allylic chlorides with boronic acids in the presence of a ruthenium catalyst, the allylic alcohols were synthesized but high regio-and enantioselectivities were not achieved. [9] Herein, we describe the direct synthesis of chiral allylic alcohols by the regio-and enantioselective allylic substitution using water as the nucleophile. [10] Previously, we reported the enantioselective allylic substitution of 1,3-disubstituted allylic carbonates with amine and carbon nucleophiles catalyzed by planar-chiral cyclopentadienyl ruthenium (Cp'Ru) complexes (1; see Table 1).…”

mentioning

confidence: 99%

Ruthenium‐Catalyzed Regio‐ and Enantioselective Allylic Substitution with Water: Direct Synthesis of Chiral Allylic Alcohols

Kanbayashi¹,

Onitsuka²

2011

Angew Chem Int Ed

View full text Add to dashboard Cite

Enantioselective allylic substitution catalyzed by transitionmetal complexes is an important process in organic synthesis.[1] For many years, mainly palladium complexes that contain chiral ligands have been employed as efficient catalysts in these reactions. Recent studies have demonstrated that chiral catalysts based on other transition metals show different regioselectivity in the synthesis of branched allylic products via monosubstituted p-allyl intermediates. [2] Although a variety of carbon and nitrogen nucleophiles can be used in those reactions, applicable oxygen nucleophiles are still limited to phenols and alcohols, which produce allylic ethers.[3] Thus, enantioenriched branched allylic alcohols, which serve as useful chiral building blocks, are often synthesized by other processes, such as the hydrogenation of a,b-unsaturated ketones, [4] the nucleophilic addition of vinylmetal reagents to aldehydes and ketones, [5] and the kinetic resolution of racemic allylic alcohols.[6] Recently, new ways to access these compounds have been developed, and they involve allylic substitution by a two-step conversion involving allylic esters and silyl ethers (Scheme 1; OPG = ester or silyl ether). [7,8] In the reaction of allylic chlorides with boronic acids in the presence of a ruthenium catalyst, the allylic alcohols were synthesized but high regio-and enantioselectivities were not achieved.[9] Herein, we describe the direct synthesis of chiral allylic alcohols by the regio-and enantioselective allylic substitution using water as the nucleophile.[10]Previously, we reported the enantioselective allylic substitution of 1,3-disubstituted allylic carbonates with amine and carbon nucleophiles catalyzed by planar-chiral cyclopentadienyl ruthenium (Cp'Ru) complexes (1; see Table 1). [11] This system was successfully extended to the regio-and enantioselective allylic substitution of monosubstituted allylic halides with oxygen and carbon nucleophiles. [12] From those studies, we found that Cp'Ru catalysts showed characteristic reactivity towards the less reactive nucleophiles. Thus, we started an examination of the enantioselective allylic substitution with water using Cp'Ru catalysts.Treatment of cinnamyl chloride (2 a) with water in the presence of 1 mol % of the Cp'Ru complex (S)-1 a resulted in the selective formation of the branched allylic alcohol (3 a; see equation in Table 1). After optimization of the reaction conditions, we found that the reaction in a mixture of THF/ water (8:1) at 25 8C with sodium hydrogen carbonate (1.2 equiv), produced 3 a after 4 hours in 99 % yield with 81 % ee.[13] Notably, the linear allylic alcohol was not formed at all. To improve the enantioselectivity, we examined the effect of the aryl groups on the phosphine ligand of the Cp'Ru catalyst (Table 1). Replacement of the phenyl groups with 3,5-dimethylphenyl and 4-methoxy-3,5-dimethylphenyl groups led to an increase in enantioselectivity to 88 % ee and 90 % ee, respectively (Table 1, entries 2 and 3). Complexes 1 d and 1 e, which have 3,...

show abstract

“…6. [27]. This reaction, which corresponds to the delivery of a nucleophile via a boron intermediate, has very few precedents in the literature, and mainly concerns the alkoxy group [28][29][30].…”

Section: Formation Of Allylic Alcohols From Boronic Acidmentioning

confidence: 98%

Ruthenium catalysts for selective nucleophilic allylic substitution

Bruneau

Renaud

Demerseman

2008

Pure and Applied Chemistry

Self Cite

View full text Add to dashboard Cite

Recent developments in the chemistry of η 3 -allylruthenium(IV) complexes are due to their straightforward synthesis resulting from oxidative addition of allylic substrates to a ruthenium(II) center. Subsequent reaction with a nucleophile is the basis of their involvement in the catalytic allylic substitution reaction. We focus here on ruthenium-catalyzed substitution of allylic substrates by C-, N-, and O-nucleophiles and show that selected ligands make regio-and enantioselective reactions possible.

show abstract

Ruthenium‐Catalyzed Synthesis of Allylic Alcohols: Boronic Acid as a Hydroxide Source

Cited by 53 publications

References 78 publications

Exploration of amino‐functionalized ionic liquids as ligand and base for Heck reaction

Exploration of amino‐functionalized ionic liquids as ligand and base for Heck reaction

Ruthenium‐Catalyzed Regio‐ and Enantioselective Allylic Substitution with Water: Direct Synthesis of Chiral Allylic Alcohols

Ruthenium catalysts for selective nucleophilic allylic substitution

Contact Info

Product

Resources

About