Deevi Basavaiah

The Baylis-Hillman reaction: A novel carbon-carbon bond forming reaction

Introduction 8002 1.1. Definition 8003 1.2. Activated alkenes--Michael-type self-dimerization 8005 Intramolecular Baylis-Hillman Reaction 8007 Mechanistic Aspects 8008 3.1. Rate enhancement 8009 3.1.1. Hydrogen bonding 8009 3.1.2. Substrate structure 8010 3.1.3. Pressure, temperature, ultrasound and microwave irradiation 8012 Asymmetric Baylis-Hillman Reaction 8013 4.1. Chiral activated alkenes 8013 4.2. Chiral electrophiles 8016 4.3. Chiral catalysts 8018 4.4. Chiral solvents 8020 4.5. Optical resolution of Baylis-Hillman adducts 8020 4.6. Masked acrylate approach to chiral Baylis-Hillman adducts 8022 Synthetic Applications 8023 5.1. Synthesis of stereodefined alkenes 8023 5.1.1. Stereoselective synthesis of [E]/[Z]-allyl halides and sulphides 8024 5.1.2. Reactions of allylic acetates, halides and sulphides 8026 5.1.2.1. Carbon nucleophiles 8026 5.1.2.2. Hydride as nucleophile 8028 5.1.2.3. Heteroatom-based nucleophiles 8029

Recent Contributions from the Baylis−Hillman Reaction to Organic Chemistry

2. Essential Components: Earlier Developments 5449 2.1. Activated alkenes/alkynes 5450 2.1.1. Acyclic activated alkenes/ alkynes 5450 2.1.2. Cyclic activated alkenes 5451 2.2. Electrophiles 5451 2.3. Catalysts 5452 3. Essential Components: Recent Developments 5452 3.1. Activated Alkenes/Alkynes 5452 3.2. Electrophiles 5460 3.3. Catalysts 5477 4. Asymmetric Baylis-Hillman Reaction: Earlier Developments 5495

The Baylis–Hillman reaction: a novel source of attraction, opportunities, and challenges in synthetic chemistry

The Baylis-Hillman reaction is a successful, useful, and atom-economical carbon-carbon bond forming reaction, which has grown from an obscure level to the level of high synthetic popularity due to its operational simplicity and also due to the enormous applications of the Baylis-Hillman adducts in organic synthesis. In this tutorial review, we briefly describe the way this reaction has grown to its present heights and the opportunities, attractions, and challenges the reaction offers with respect to its asymmetric and intramolecular versions, and mechanistic aspects.

A simple synthesis of α- methylene - β- hydroxyalkanones

Abstract Reaction of methyl vinyl ketone with a variety of aldehydes, catalyzed by 1,4-diazabicyclo (2.2.2)octane (DABCO) in tetrahydrofuran, conveniently provides the corresponding α-methylene-β-hydroxyalkanones in good yields.

DABCO catalyzed dimerization of α,β-unsaturated ketones and nitriles

Abstract α,β-Unsaturated ketones dimerize in the presence of catalytic amount of 1,4-diazabicyclo[2.2.2]octane(DABCO) to produce the corresponding 2-methylene-1,5-diketones in good yields. Acrylonitrile provides the corresponding dimerized product.

DABCO catalyzed coupling of α-keto esters with acrylonitrile and methyl acrylate

Abstract Coupling of acrylonitrile to α-keto esters is readily achieved using 1,4-diazabicyclo[2.2.2]-octane(DABCO) as a catalyst to produce 2-[1-carboalkoxy-1-hydroxyalkyl]acrylonitriles in good yields. Similar reaction with methyl acrylate produces the corresponding 2-substituted acrylates.

Chiral acrylates as substrates in baylis-hillman reaction

Abstract DABCO induces diastereoselective (7–70%) coupling of chiral acrylates (1–3) with aldehydes to produce the corresponding 2-(1-hydroxyalkyl)acrylates.

Applications of Baylis–Hillman chemistry: one-pot convenient synthesis of functionalized (1H)-quinol-2-ones and quinolines

A simple synthesis of functionalized (1H)-quinol-2-ones and quinolines from the Baylis-Hillman adducts, i.e. alkyl 3-hydroxy-2-methylene-3-arylpropanoates and β-hydroxy-a-methylene-β-arylalkanones, respectively, has been described.

Baylis-Hillman chemistry: a novel synthesis of functionalized 1,4-pentadienes

Abstract A novel synthesis of functionalized 1,4-pentadienes via the reaction of acrylonitrile with allyl halides, derived from Baylis–Hillman adducts, in the presence of DABCO has been described, demonstrating for the first time the application of allyl halides as electrophiles in the Baylis–Hillman reaction.

First example of electrophile induced Baylis–Hillman reaction: a novel facile one-pot synthesis of indolizine derivativesElectronic supplementary information (ESI) available: Experimental procedures, analytical and spectral data for all the compounds 2a–i. See http://www.rsc.org/suppdata/cc/b2/b211349j/

Treatment of pyridine-2-carboxaldehyde with activated alkenes such as alkyl vinyl ketones and cyclic enones in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) provides a novel facile one-pot synthesis of indolizine derivatives, thus for the first time describing an electrophile induced Baylis-Hillman reaction.