Synthesis Of Homoallylic Alcohols Research Articles

Overcoming the Usual Reactivity of β-Nitroenones: Synthesis of Polyfunctionalized Homoallylic Alcohols and Conjugated Nitrotriene Systems

Herein, we report a new application of β-nitroenones as valuable building blocks for the preparation of polyfunctionalized homoallylic alcohols; they can be used as key precursors of conjugated nitrotriene systems. The synthesis of homoallylic alcohols was performed exploiting the chemoselective addition of metal allylating agents to the ketone moiety vs the nitroalkenyl group. The conversion of alcohols into nitrotrienes was achieved under Lewis-acid-promoted conditions. Both classes of compounds were obtained in good to excellent yields.

Nickel-Catalyzed Synthesis of Homoallylic Alcohols under Photoredox Conditions

Nickel-Catalyzed Synthesis of Homoallylic Alcohols under Photoredox Conditions

Copper‐Impregnated Magnesium‐Lanthanum Mixed Oxide: A Reusable Heterogeneous Catalyst for Allylation of Aldehydes and Ketones

AbstractCopper‐impregnated magnesium‐lanthanum mixed oxide [Cu(II)/Mg−La] was used as catalyst in synthesis of homoallylic alcohols from aldehydes and ketones using allyltributylstannane as the allylating source. The present protocol provides a great application potential for the synthesis of corresponding allyl alcohols with excellent yields and selectivity. The catalyst exhibits broad functional group compatibility with a variety of substituted aldehydes and ketones to furnish the desired products in high yields under heterogeneous conditions. Importantly, the heterogeneous catalyst could be recovered from the reaction mixture by centrifugation and used up to three cycles.magnified image

Synthesis of Homoallylic Alcohols with Acyclic Quaternary Centers through CoIII -Catalyzed Three-Component C-H Bond Addition to Internally Substituted Dienes and Carbonyls.

An efficient CoIII -catalyzed three-component strategy to prepare homoallylic alcohols containing acyclic quaternary centers is disclosed. This transformation enables the introduction of two C-C σ bonds through C-H bond activation and sequential addition to internally substituted dienes and a wide range of aldehydes and activated ketones. Isoprene and other internally monosubstituted dienes are effective inputs, with the reaction proceeding with high diastereoselectivity for those substrate combinations that result in more than one stereogenic center. Moreover, the opposite relative stereochemistry can be achieved by employing 1,2-disubstituted dienes. A mechanism for the transformation is proposed based upon the relative stereochemistry of the products and studies with isotopically labeled starting materials.

Synthesis of Homoallylic Alcohols with Acyclic Quaternary Centers through CoIII‐Catalyzed Three‐Component C−H Bond Addition to Internally Substituted Dienes and Carbonyls

AbstractAn efficient CoIII‐catalyzed three‐component strategy to prepare homoallylic alcohols containing acyclic quaternary centers is disclosed. This transformation enables the introduction of two C−C σ bonds through C−H bond activation and sequential addition to internally substituted dienes and a wide range of aldehydes and activated ketones. Isoprene and other internally monosubstituted dienes are effective inputs, with the reaction proceeding with high diastereoselectivity for those substrate combinations that result in more than one stereogenic center. Moreover, the opposite relative stereochemistry can be achieved by employing 1,2‐disubstituted dienes. A mechanism for the transformation is proposed based upon the relative stereochemistry of the products and studies with isotopically labeled starting materials.

Palladium-Catalyzed Diastereoselective Synthesis of Homoallylic Alcohols

Palladium-Catalyzed Diastereoselective Synthesis of Homoallylic Alcohols

Copper-Catalyzed Synthesis of Homoallylic Alcohols

Copper-Catalyzed Synthesis of Homoallylic Alcohols

Efficient Synthesis of Homoallylic Alcohols/Amines from Allyltributylstannane and Carbonyl Compounds/Imines Using Iodine as Catalyst Under Acetic Acid–Water Medium

This paper describes a general method for the synthesis of homoallylic alcohols and amines by nucleophilic addition reaction of allyltributylstannane to carbonyl compounds and aldimines where iodine acts as a catalyst in H2O/acetic acid (1:1) medium. Only 10 mol% of I2 is required for various organic transformations. By using this process, various homoallylic alcohols and amines are produced in good to excellent yields.

Metal free synthesis of homoallylic alcohols promoted by ultrasound

The use of ultrasound irradiation to promote the allylation of aldehydes containing different functionalities with potassium allyltrifluoroborates is described. The method features the use of a minimum amount of acetone as solvent, without any other catalyst or promoter. The products were obtained in high yields, short reaction times, at room temperature and without the need of further purification.

ChemInform Abstract: Indium‐Mediated Synthesis of Homoallyl Alcohols in the Aqueous Phase.

Abstract The indium-mediated Barbier-type allylation reaction of aldehydes with allyl bromide, which gives corresponding homoallyl alcohols, was investigated. The reaction medium and the effects of substituents were discussed in detail. The results showed that various aldehydes, including aromatic, heterocyclic, and aliphatic aldehydes, with different substituents could all react well with excellent yields of 91–97% in aqueous tetrahydrofuran at room temperature within about 1 h.

Indium-Mediated Synthesis of Homoallyl Alcohols in the Aqueous Phase

The indium-mediated Barbier-type allylation reaction of aldehydes with allyl bromide, which gives corresponding homoallyl alcohols, was investigated. The reaction medium and the effects of substituents were discussed in detail. The results showed that various aldehydes, including aromatic, heterocyclic, and aliphatic aldehydes, with different substituents could all react well with excellent yields of 91–97% in aqueous tetrahydrofuran at room temperature within about 1 h.

Fumonisin: A template for methodology development and drug discovery

The chemistry and biology of the fumonisin family of natural products has inspired an integrated research program featuring methods development for stereoselective synthesis of homoallylic alcohols, accompanied by applications of these methods to the first synthesis of fumonisin B1, and to preparing a family of stereoisomeric 2-amino-3,5-diol analogs of 1-deoxysphingolipids, as a possible approach to discovering new drugs for cancer chemotherapy.

Iridium-Catalyzed Reactions Involving Transfer Hydrogenation, Addition, N-Heterocyclization, and Alkylation Using Alcohols and Diols as Key Substrates

This account gives an overview of iridium-catalyzed -reactionsdeveloped by our group using mainly alcohols and diols as substrates.In the presented reactions, the iridium catalyst serves as a hydrogenacceptor from the alcohols giving iridium hydride, which is a keytransient species. Herein, we report hydrogenation, alkylation,esterification, N-heterocyclization, and coupling reactions usingalcohols and diols as reagents. 1 Introduction 2 Hydrogenation of α,β-Unsaturated CarbonylCompounds and Alkenes 3 Synthesis of Vinyl and Allyl Ethers 4 Synthesis of γ,δ-Unsaturated Carbonyl Compounds 5 α-Alkylation Using Alcohols and Diols as Alkylating Agents 5.1 α-Alkylation of Methyl Ketones 5.2 α-Alkylation of Arylacetonitriles 5.3 α-Alkylation of Active Methylene Compounds 5.4 α-Alkylation of Acetates 6 β-Alkylation (Guerbet Reaction) 7 Oxidative Esterification 8 N-Heterocyclization 8.1 Synthesis of Quinolines from Amino Alcohols and Ketones 8.2 Synthesis of Benzo[ H]quinolinesand Benzoindole Derivatives from Naphthylamines and Diols 9 Coupling Reaction of Alcohols with Alkynes 9.1 Synthesis of Homoallylic Alcohols 9.2 Synthesis of α,β-Unsaturated Ketones (Hydroacylation) 10 Concluding Remarks

ChemInform Abstract: The Reaction of β-(Trimethylsilyl)alkyl Phenyl Sulfones with Oxiranes. A Method for Stereocontrolled Synthesis of Homoallylic Alcohols.

Abstract The reaction of β-trimethylsilylalkyl sulfones ( 4a – 4b ) with oxirane derivatives ( 5a – 5d , 9 ) followed by treatment of the immediate adducts with sodium hydride, affords O-trimethylsilyl homoallylic alcohols ( 7a – 7e , 11 ), mainly (Z) isomers.

ChemInform Abstract: Synthesis of Homoallylic Alcohols (III), (IV), (VI), (VII) via Palladium-Catalyzed Cross-Coupling of Vinylic Oxetanes (II) and Aryl and Vinylic Iodides or Triflates (I), (V).

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Stereoselective Synthesis of Homoallylic Alcohols of the [2.2]Paracyclophane Series and Their Use as Auxiliaries in Asymmetric Allylboration of Aldehydes.

Stereoselectivity of allylboration of 4-formyl[2.2]paracyclophane, 4-acetyl[2.2]paracyclophane, and 4-hydroxy-5-formyl[2.2]paracyclophane was studied and the relative configurations of the homoallylic alcohols obtained were established. Optically pure (Sp,Sc)-(+)-4-(4-hydroxy-1-methylbut-3-enyl)[2.2]paracyclophane and (Rc,Sc)-(+)-4-hydroxy-5-(4-hydroxybut-3-enyl)[2.2]paracyclophane were synthesized. The possibility of using (Sp,Sc)-(+)-4-(4-hydroxy-4-methylbut-3-enyl)[2.2]paracyclophane as a recoverable chiral auxiliary in asymmetric allylboration of aldehydes was demonstrated.

Mg(NTf2)2·xH2O: An Efficient Catalyst for the Synthesis of Homoallylic Alcohols in Water

An efficient method has been developed for the allylation of aldehydes with allytributylstannane in the presence of a catalytic amount of Mg(NTf2)2·xH2O at room temperature in water to afford the corresponding homoallylic alcohols in good yields.

ChemInform Abstract: Synthesis of Homoallylic Alcohols via Lewis Acid Assisted Enantioselective Desymmetrization.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of homoallylic alcohols by allylation of aldehydes and ketones catalysed by a mesoporous material (MCM-41)-supported cyano palladium complex

A variety of homoallylic alcohols has been conveniently synthesised in good to high yields by the allylation of aldehydes and ketones with allylic chlorides catalysed by an MCM-41-supported cyano palladium complex in DMF using SnCl2 as reducing agent. This polymeric palladium complex can be recovered and reused with some loss of activity.

Synthesis of Homoallylic Alcohols via Lewis Acid Assisted Enantioselective Desymmetrization

A highly enantioselective allylic substitution of (Z)-but-2-ene-1,4-diol derivatives was developed using a rhodium(I) catalyst and arylboronic acids as nucleophiles. The reaction yields versatile homoallylic alcohols from readily available linear biscarbonates.