Conversion of Phenols and Anilines to -Olefins via Oxidation, Wittig Olefination, and Stereoselective Olefin Isomerization.

Development of metal-free conversion of naturally abundant phenols and anilines to the corresponding olefins remains a formidable challenge. The current state of the art relies on the TM-catalyzed Heck coupling of activated phenols (triflates, tosylates, and more) with the olefins. While these advancements are promising, the reaction suffers from branch vs linear selectivity and requires an expensive TM-ligand combination, hazardous organotin reagents, and very high reaction temperature.

Alkoxide-Assisted Stereoselective Functionalization of 1,2-Bis-boronic Esters Under Photoredox Catalysis.

Site-specific functionalization of the secondary C-B bond of 1,2-bis-boronic esters has been proven to be an important method for the generation of 1,2-bis-functionalized compounds in a highly stereoselective manner. We have explored previously unknown secondary selective alkenylation, allylation, alkynylation and addition to aryl vinyl trifluoromethane, which proceeds via a novel reaction mechanism: alkoxide-mediated photoredox activation to generate secondary radicals over the primary one.

One pot conversion of phenols and anilines to aldehydes and ketones exploiting α gem boryl carbanions.

Functional group interconversion is an important asset in organic synthesis. Phenols/anilines being naturally abundant and the carbonyl being the most common in a wide range of bioactive molecules, an efficient conversion is of prime interest. The reported methods require transition metal catalyzed cross coupling which limits its applicability.

Reactivity of 1,3-enyne MIDA boronates: exploration of novel 1,2-alkyne shift -difluorination.

The discovery of a new class of heteroatom-rich boron-containing molecules (BCMs) and iterative cross-coupling (ICC) partners created a toolbox for future drug developments using organoboron compounds. Herein, we report the potential utility of 1,3-enyne MIDA boronates to access diverse -difluoro MIDA boronates novel 1,2-alkyne shift. This unique reactivity of 1,3-enyne MIDA boronates offers facile access to previously challenging β-difluorinated alkyl borons.

Synthesis of Boronic Esters from Organometallic Reagents and Bis(pinacolato)diboron.

Synthesis of alkyl, aryl, and vinyl boronic esters carrying various chiral and achiral diol-protecting groups were synthesized starting from the corresponding alkyl, aryl, and vinyl lithium or Grignard reagents. Good to excellent yields were obtained for a large range of substrates. The reaction can be conducted in a gram scale to obtain the product over 80 % yield.

Stereoselective Synthesis of Silylated Vinylboronates by a Boron-Wittig Reaction and Their Application to Tetrasubstituted Olefins.

The highly stereoselective synthesis of a series of tetrasubstituted mono- as well as disilylated vinylboronates is reported by using the boron-Wittig approach. The condensation between acylsilanes and gem-diborylalkanes gave the desired tetrasubstituted olefins in good to excellent yield and high stereoselectivity. Also, a series of trisubstituted silylated vinyl MIDA-boronates was synthesized by using the boron-Wittig reaction followed by a transesterification reaction.

Carbonyl group directed synthesis of 3-boryl-3-substituted alkenyl oxindoles and tetrasubstituted β-borylenones.

Transition metal-free carbonyl directed boron-Wittig reaction of α-bis(boryl)carbanions with the corresponding isatins or with the α-keto esters/amides was achieved to access alkenyl oxindoles in good yield and high stereoselectivity.

Stereodivergent Zweifel Olefination and its Mechanistic Dichotomy.

Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π-systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3-dienes in good yield and up to 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z-vinyl heteroarenes for different heteroarenes under identical conditions.

1,2-Metallate Rearrangement Using Indole Boronate Species to Access 2,3-Diarylindoles and Indolines.

A transition metal-free multicomponent reaction using lithiated indole, boronic ester, pyridine, and ethyl chloroformate was developed to access C2,C3 bis-arylated indoles, which are present in several marketed drugs and bioactive compounds. One-pot access to unsymmetrical C2,C3-diaryl indole from the parent indole remains a huge synthetic challenge. Our group was able to achieve this goal through a transition metal-free 1,2-metalate rearrangement of the indole boronate complex.

Recent advances in the synthesis and reactivity of MIDA boronates.

Organoboron compounds have a wide-range of applications in synthetic methodologies, natural products, and bioactive molecule synthesis. The sensitivity of boronic acid toward most synthetic reagents makes it necessary to introduce a protecting group before its utilization. Benchtop stable MIDA boronates have been found compatible with various common synthetic reagents which opens the doors for the synthesis of various small building blocks, natural products, and bioactive compounds.

Iron Catalysis: A New Horizon Towards Organoboron-mediated C-C Cross-coupling.

Transition metal-catalyzed cross-couplings have had a profound impact on chemical synthesis. Among the various transition metals, iron has drawn huge attention due to its cost effectiveness, range of stable oxidation states, Lewis acidic property and releatively less toxicity. Iron complexes have exhibited an efficient catalytic activity towards the cross-coupling reaction using organomagnesium, organolithium and organozinc reagent.

Mechanistic dichotomy in the solvent dependent access to -allylic amines decarboxylative vinylation of amino acids.

The solvent plays an important role in the photophysical properties of donor-acceptor based photocatalysts. The solvent-dependent access to -allylic amines was achieved decarboxylative vinylation of amino acids with vinyl sulfones. Detailed experimental studies have been conducted to understand the role of the solvent in the reactivity and stereoselectivity of the vinylation reactions.

Development of homologous hemizona assay as a potential predictor of fertility in buffalo bulls: A preliminary approach.

Although, myriads of tests are routinely used, no single test can accurately predict fertilization potential of semen. The hemizona assay (HZA) has advantages in two ways: (a) it determines multitude traits of sperm and (b) it is a controlled sperm function test. In the present study, we developed homologous HZA in buffaloes to predict bull fertility.

Transition-Metal-Free Heterocyclic Carbon-Boron Bond Formation.

Heteroaryl boronic acids and esters are extremely important and valuable intermediates because of their wide application in the synthesis of marketed drugs and bioactive compounds. Over the last couple of decades, the construction of highly important heteroaryl carbon-boron bonds has created huge attention. The transition-metal-free protocols are more green, less sensitive to air and moisture, and also economically advantageous over the transition-metal-based protocols.

Development of Methods to the Synthesis of β-Boryl Acyls, Imines and Nitriles.

Organoboron compounds are highly important and versatile synthetic intermediates for the preparation of a wide range of organic molecules. Organoboron compounds have drawn significant attention among organic chemists due to their Lewis acidic property, non-toxicity, and commercial availability. Over the last several decades, there has been a substantial development of new organoboron compounds, useful in organic synthesis.

Recombinant expression and molecular characterization of buffalo sperm lysozyme-like protein 1.

Several sperm lysozyme-like genes evolved from lysozyme by successive duplications and mutations; however their functional role in the reproduction of farm animals is not well understood. To understand the function and molecular properties of buffalo sperm lysozyme-like protein 1 (buSLLP1), it was expressed in E. coli; however, it partitioned to inclusion bodies.

Synthesis and reactivity of alkynyl boron compounds.

Over the last century, there have been considerable developments in organoboron chemistry due to the stability, non-toxicity, and easy commercial availability of various boronic esters. Several organoboron reagents have emerged and play an increasingly important role in everyday organic synthesis. Among them, alkynyl boron compounds have attracted significant attention due to their easy synthesis and diverse reactivity.

Transition metal catalyzed asymmetric multicomponent reactions of unsaturated compounds using organoboron reagents.

Asymmetric multicomponent reactions allow stitching several functional groups in an enantioselective and atom economical manner. The introduction of boron-based reagents as a multicomponent coupling partner has its own merits. In addition to being non-toxic and highly stable, organoboron compounds can be easily converted to other functional groups in a stereoselective manner.

Transition metal-free synthesis of alkyl pinacol boronates.

Alkyl pinacol boronic esters have been routinely used for the synthesis of complex target molecules or high-value chemicals due to their non-toxicity, stability and commercial availability. The synthesis of C-B bonds in the absence of transition metals has gained significant attention due to its added advantages. Numerous methods have been developed for the synthesis of alkyl pinacol boronates without transition metals, which include reactions using organometallic reagents, Lewis acids and bases, photoredox catalysis, and 1,2-metallate rearrangement.

Functionalization of Heterocycles through 1,2-Metallate Rearrangement of Boronate Complexes.

Over the last decade, 1,2-metallate rearrangement of boronate complex has been dominating the literature of organoboron chemistry for the construction of very important C-C and C-boron bonds. Owing to the coordinative unsaturated nature of the boron atom, a nucleophile can attack on boron center for the formation of a boronate complex, which triggers 1,2-migration under electrophilic activation at the α-carbon. Apart from using stochiometric electrophilic activating reagents, several catalytic methods using transition metals in the presence or absence of light have been reported.

Transition-Metal-Free Synthesis of Heterobiaryls through 1,2-Migration of Boronate Complex.

The synthesis of a diverse range of heterobiaryls has been achieved by a transition-metal-free sp -sp cross-coupling strategy using lithiated heterocycle, aryl or heteroaryl boronic ester and an electrophilic halogen source. The construction of heterobiaryls was carried out through electrophilic activation of the aryl-heteroaryl boronate complex, which triggered 1,2-migration from boron to the carbon atom. Subsequent oxidation of the intermediate boronic ester afforded heterobiaryls in good yield.

Tandem Allylation/1,2-Boronate Rearrangement for the Asymmetric Synthesis of Indolines with Adjacent Quaternary Stereocenters.

A three-component coupling using lithiated indoles, boronate esters and allylic acetates generates chiral indolines with adjacent quaternary stereocenters. Successful stereocontrol required the use of phosphoramidite ligands not previously described for organopalladium chemistry. Mechanistic studies indicate a monodentate PdL intermediate, and a stepwise allylation-aryl/alkyl migration.

Palladium Catalyzed Asymmetric Three-Component Coupling of Boronic Esters, Indoles, and Allylic Acetates.

Boronic esters react with 2-lithiated indoles to form boronate intermediates. The boronate reacts with allylic acetates in the presence of (BINAP)Pd catalysts to allylate C3 concurrent with alkyl migration from B to C2 of the indole. Overall, the process is a three-component coupling that joins an allylic acetate, and indole and an organo-B(pin) species to provide substituted indoles and indolines with high enantio-, regio-, and diastereoselectivity.

Synthesis and Utility of Dihydropyridine Boronic Esters.

When activated by an acylating agent, pyridine boronic esters react with organometallic reagents to form a dihydropyridine boronic ester. This intermediate allows access to a number of valuable substituted pyridine, dihydropyridine, and piperidine products.

In vitro culture of functionally active buffalo hepatocytes isolated by using a simplified manual perfusion method.

Background: In farm animals, there is no suitable cell line available to understand liver-specific functions. This has limited our understanding of liver function and metabolism in farm animals. Culturing and maintenance of functionally active hepatocytes is difficult, since they survive no more than few days.