Rhodium-Catalyzed Regioselective [4 + 2] Cycloaddition of Ynamines and 2-(Cyanomethyl)phenylboronates.

A rhodium-catalyzed [4 + 2] cycloaddition of ynamines and 2-(cyanomethyl)phenylboronates has been developed, leading to efficient and excellent regioselective synthesis of valuable indole-linked aromatic compounds in a concise and flexible approach. Interestingly, this strategy was successful in the construction of C···N axially chiral indoles with high enantiocontrol by the introduction of a new phosphoramidite ligand (Xie-Phos).

Congested C(sp3)-rich architectures enabled by iron-catalysed conjunctive alkylation.

Catalytic cross-coupling by transition metals has revolutionized the formation of C-C bonds in organic synthesis. However, the challenge of forming multiple alkyl-alkyl bonds in crowded environments remains largely unresolved. Here, we report the regioselective functionalization of olefins with sp-hybridized organohalides and organozinc reagents using a simple (terpyridine)iron catalyst.

Effects of Five Dietary Carbohydrate Sources on Growth, Glucose Metabolism, Antioxidant Capacity and Immunity of Largemouth Bass ().

This study investigated the effects of glucose (GLU), tapioca starch (TS), gelatinized tapioca starch (GTS), potato starch (PS) and gelatinized potato starch (GPS) on growth and physiological responses in juvenile largemouth bass . After 8 weeks, fish fed with starch diets had better weight gain and growth rates. Counts of red blood cells and monocytes were increased in the PS and GPS groups, compared to GLU group.

Ir/Zn-cocatalyzed chemo- and atroposelective [2+2+2] cycloaddition for construction of C─N axially chiral indoles and pyrroles.

Here, an Ir/Zn-cocatalyzed atroposelective [2+2+2] cycloaddition of 1,6-diynes and ynamines was developed, forging various functionalized C─N axially chiral indoles and pyrroles in generally good to excellent yields (up to 99%), excellent chemoselectivities, and high enantioselectivities (up to 98% enantiomeric excess) with wide substrate scope. This cocatalyzed strategy not only provided an alternative promising and reliable way for asymmetric alkyne [2+2+2] cyclotrimerization in an easy handle but also settled the issues of previous [Rh(COD)]BF-catalyzed system on the construction of C─N axial chirality such as complex operations, limited substrate scope, and low efficiency. In addition, control experiments and theoretical calculations disclosed that Zn(OTf) markedly reduced the barrier of migration insertion to significantly increase reaction efficiency, which was distinctly different from previous work on the Lewis acid for improving reaction yield through accelerating oxidative addition and reductive elimination.

Copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations.

The enantioselective transformation of easily accessible 1,2-diketones represents a quick pathway towards enantioenriched molecules. Herein, we disclose a copper-catalyzed atroposelective formal [4+1] annulation of 1,2-diketones with vinyl cations, enabling the efficient and atom-economical construction of axially chiral arylpyrroles bearing 1,3-dioxole moieties with good to excellent enantioselectivities under mild reaction conditions. Importantly, this methodology constitutes the first enantioselective formal [4+1] annulation of 1,2-diketones.

Ruthenium-Catalyzed 1,6-Hydroalkylation of -Quinone Methides with Ketones via the Activation of C()-H Bonds.

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of -quinone methides (-QMs) with ketones via the activation of C()-H bonds has been disclosed. Without the need for preactivation of the substrates and oxidant, a broad range of -QMs and ketones are well tolerated, producing the expected 1,6-hydroalkylation products with moderate to good yields. Step-by-step control experiments and DFT calculation were conducted systematically to gain insights for the plausible reaction mechanism.

Copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles.

One-carbon homologation reactions based on one-carbon insertion into the N-O bond of heterocycles have received tremendous interest over the past decades. However, these protocols have to rely on the use of hazardous and not easily accessible diazo compounds as precursors, and examples of the relevant asymmetric catalysis have not been reported. Here we show that a copper-catalyzed intermolecular formal (5 + 1) annulation of 1,5-diynes with 1,2,5-oxadiazoles involving one-carbon insertion into the heterocyclic N-O bond via non-diazo approach.

Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles.

A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles the Michaelis-Arbuzov rearrangement for the synthesis of β-ketophosphine oxides, β-ketophosphinates, and β-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles are tolerated in the transformation, generating the desired β-keto-organophosphorus compounds as a valuable class of phosphorus-containing intermediates with good to excellent yields.

Copper-Catalyzed Tandem Cyclization/Direct C(sp)-H Annulation of Azide-Ynamides via α-Imino Copper Carbenes: Access to Azepino[2,3-:4,5-']diindoles.

A novel copper-catalyzed tandem cyclization/direct C(sp)-H annulation of phenyl azide-ynamides via α-imino copper carbenes has been developed, which provides a concise and flexible approach for the construction of a range of valuable azepino[2,3-:4,5-']diindoles in mostly good to excellent yields with high chemoselectivities. This tandem reaction also exhibits a broad substrate scope, excellent functional group tolerance, simple operation, and mild reaction conditions.

Brønsted acid-catalyzed asymmetric dearomatization for synthesis of chiral fused polycyclic enone and indoline scaffolds.

In the past two decades, substantial advances have been made on the asymmetric alkyne functionalization by the activation of inert alkynes. However, these asymmetric transformations have so far been mostly limited to transition metal catalysis, and chiral Brønsted acid-catalyzed examples are rarely explored. Here, we report a chiral Brønsted acid-catalyzed dearomatization reaction of phenol- and indole-tethered homopropargyl amines, allowing the practical and atom-economical synthesis of a diverse array of valuable fused polycyclic enones and indolines bearing a chiral quaternary carbon stereocenter and two contiguous stereogenic centers in moderate to good yields with excellent diastereoselectivities and generally excellent enantioselectivities (up to >99% enantiomeric excess).

I -Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives.

Herein, an I -catalyzed unprecedented cycloisomerization of ynamides is developed, furnishing various functionalized bis(indole) derivatives in generally good to excellent yields with wide substrate scope and excellent atom-economy. This protocol not only represents the first molecular-iodine-catalyzed tandem complex alkyne cycloisomerizations, but also constitutes the first chemoselective cycloisomerization of tryptamine-ynamides involving distinctively different C(sp )-C(sp ) bond cleavage and rearrangement. Moreover, chiral tetrahydropyridine frameworks containing two stereocenters are obtained with moderate to excellent diastereoselectivities and excellent enantioselectivities.

Highly Site-Selective Oxidative Cyclization of Ene-ynamides via Non-Noble-Metal Catalysis: Access to Functionalized Lactams.

Herein, an unprecedented non-noble-metal-catalyzed oxidation/cyclization of ene-ynamides is developed, allowing the synthesis of diversely functionalized lactams in moderate to good yields with excellent diastereoselectivities without the observation of typical cyclopropanation products. In combination with Ellman's -butylsulfinimine chemistry, chiral γ-lactams containing three contiguous stereocenters are obtained with high diastereo- and enantioselectivity. Moreover, density functional theory (DFT) calculations indicate that this protocol probably undergoes a carbon cation or proton transfer process.

Enantioselective Rh-Catalyzed Azide-Internal-Alkyne Cycloaddition for the Construction of Axially Chiral 1,2,3-Triazoles.

Significant advances have been achieved for the construction of chiral skeletons containing 1,2,3-triazoles via transition-metal-catalyzed asymmetric azide-alkyne cycloaddition; however, most of them have been limited to terminal alkynes in the synthesis of central chirality via desymmetrization and dynamic/dynamic kinetic resolution. Enantioselective transition-metal-catalyzed azide-internal-alkyne cycloaddition is extremely limited. Moreover, the construction of a challenging five-membered (hetero)biaryl axially chiral molecule via transition-metal-catalyzed asymmetric azide-internal-alkyne cycloaddition is still underexplored.

Catalytic enantioselective reductive domino alkyl arylation of acrylates via nickel/photoredox catalysis.

Nonsteroidal anti-inflammatory drug derivatives (NSAIDs) are an important class of medications. Here we show a visible-light-promoted photoredox/nickel catalyzed approach to construct enantioenriched NSAIDs via a three-component alkyl arylation of acrylates. This reductive cross-electrophile coupling avoids preformed organometallic reagents and replaces stoichiometric metal reductants by an organic reductant (Hantzsch ester).

Gold-catalysed asymmetric net addition of unactivated propargylic C-H bonds to tethered aldehydes.

The asymmetric one-step net addition of unactivated propargylic C-H bond to aldehyde leads to an atom-economic construction of versatile chiral propargylic alcohols but has not been realized previously. Here we show its implementation in an intramolecular manner under mild reaction conditions. Via cooperative gold catalysis enabled by a chiral bifunctional phosphine ligand, this chemistry achieves asymmetric catalytic deprotonation of propargylic C-H (pK > 30) by a tertiary amine group (pK ~ 10) of the ligand in the presence of much more acidic aldehydic α-hydrogens (pKa ~ 17).

Regio- and diastereoselective synthesis of trans-3,4-diaryldihydrocoumarins via metal-free [4+2] annulation of ynamides with o-hydroxybenzyl alcohols.

An efficient regio- and diastereoselective method for the construction of valuable trans-3,4-diaryldihydrocoumarins via metal-free [4+2] annulation of ynamides with o-hydroxybenzyl alcohols has been developed. Ynamides are first treated as 2-π partners to react with o-hydroxybenzyl alcohols via traceless sulfonamide directing groups, affording trans-3,4-diaryldihydrocoumarins in good yields with high regio- and diastereoselectivities. This metal-free methodology is also characterized by a wide substrate scope, good functional group tolerance, and efficiency on a gram scale.

Vinylene carbonate: beyond the ethyne surrogate in rhodium-catalyzed annulation with amidines toward 4-methylquinazolines.

In this paper, we developed a rhodium-catalyzed annulation of vinylene carbonate with amidines, leading to 4-methylquinazolines with moderate to excellent yields. This procedure proceeded by sequential ortho-acylation and annulation, where vinylene carbonate served as the acetylation reagent rather than the ethyne surrogate.

Palladium-Catalyzed Direct Arylation of 2-Pyridylmethyl Silanes with Aryl Bromides.

The first palladium-catalyzed direct arylation of 2-pyridylmethyl silanes with aryl bromides to generate a diverse array of aryl(2-pyridyl)-methyl silane derivatives has been developed. This protocol facilitates access to various kinds of heterocycle-containing silanes in good to excellent yields (40 examples, 66-97% yield) with good functional group tolerance. The scalability of this transformation is demonstrated.

Cyanoalkylation/alkynylation of allylic alcohol through intramolecular radical 1,2-alkynyl migration.

A di-tert-butyl peroxide (DTBP)-promoted difunctionalization of α-aryl α-alkynyl allylic alcohols with alkyl nitriles was developed, affording a series of α-alkynyl γ-cyano functionalized ketones in moderate yields. This procedure involved C(sp)-H bond cleavage of alkyl nitriles and radical 3-exo-dig cyclization. After this, radical 1,2-alkynyl migration is preferred rather than 1,2-aryl migration.

Solar-Driven Hydrogen Generation Catalyzed by g-CN with Poly(platinaynes) as Efficient Electron Donor at Low Platinum Content.

A metal-complex-modified graphitic carbon nitride (g-CN) bulk heterostructure is presented here as a promising alternative to high-cost noble metals as artificial photocatalysts. Theoretical and experimental studies of the spectral and physicochemical properties of three structurally similar molecules , , and confirm that the Pt(II) acetylide group effectively expands the electron delocalization and adjusts the molecular orbital levels to form a relatively narrow bandgap. Using these molecules, the donor-acceptor assemblies @, @, and @ are formed with g-CN.

Recent advances in the Rh-catalyzed cascade arene C-H bond activation/annulation toward diverse heterocyclic compounds.

The Rh-catalyzed C-H bond activation/annulation provides a new strategy for the synthesis of new frameworks. In this review, we summarize the recent research on the Rh-catalyzed cascade arene C-H bond activation/annulation toward diverse heterocyclic compounds. The application, scope, limitations and mechanism of these transformations are also discussed.

The intramolecular reaction of acetophenone -tosylhydrazone and vinyl: Brønsted acid-promoted cationic cyclization toward polysubstituted indenes.

In the presence of TsNHNH2, a Brønsted acid-promoted intramolecular cyclization of o-(1-arylvinyl) acetophenone derivatives was developed, leading to polysubstituted indenes with complexity and diversity in moderate to excellent yields. In sharp contrast with either the radical or carbene involved cyclization of aldehydic N-tosylhydrazone with vinyl, a cationic cyclization pathway was involved, where N-tosylhydrazone served as an electrophile and alkylation reagent during this transformation.

Recent Progress in the Selective Functionalization of P(O)-OH Bonds.

As we all know, organic phosphorus compounds have high application values in chemical industries. Compared with traditional compounds with P-X (X = Cl, Br, I) and P-H bonds, phosphorylation reagents containing P(O)-OH bonds are stable, environmentally friendly, and inexpensive. However, in recent years, there have been few studies on the selective functionalization of P(O)-OH bonds for the fabrication of P-C and P-Z bonds.