Triacontanol delivery by nano star shaped polymer promoted growth in maize.

Plant Growth Regulators (PGRs) are functional compounds known for enhancing plant growth and development. However, their environmental impact is a concern due to poor water solubility and the need for substantial organic solvents. Recently, nano-delivery systems have emerged as a solution, offering a broad range of applications for small molecule compounds. This study introduces a nano-delivery system for Triacontanol (TA), utilizing a star polymer (SPc), aimed at promoting maize growth and improving physiological indicators. The system forms nearly spherical nanoparticles through TA's hydroxyl group and SPc's tertiary amine group. The TA/SPc nano-complex notably outperforms separate TA or SPc treatments in maize, increasing biomass, chlorophyll content, and nutrient absorption. It elevates chlorophyll content by 16.4%, 10.0%, and 6.2% over water, TA, and SPc treatments, respectively, and boosts potassium and nitrate ion uptake by up to 2 and 1.6 times compared to TA alone, leading to enhanced plant height and leaf growth. qRT-PCR analysis further demonstrated that the nano-complex enhanced cellular uptake through the endocytosis pathway by up-regulating endocytosis-related gene expression. The employment of TEM to observe vesicle formation during the internalization of maize leaves furnishes corroborative evidence for the participation of the endocytosis pathway in this process. This research confirms that SPc is an effective carrier for TA, significantly enhancing biological activity and reducing TA dosage requirements.

Synthesis of triarylmethanes by silyl radical-mediated cross-coupling of aryl fluorides and arylmethanes.

Although the cross-couplings of aryl halides with diarylmethanes are mostly achieved by transition-metal catalysis, aryl fluorides are rarely used as coupling partners owing to the high inertness of C-F bonds. Herein, we describe the efficient silylboronate-mediated cross-coupling reaction of aryl fluorides with arylalkanes under transition-metal-free, room-temperature conditions. The combination of silylboronate and KO t Bu is critical for driving a radical process via the cleavage of C-F and C-H bonds in two appropriate coupling precursors, resulting in a cross-coupling product. This practical cross-coupling protocol is applicable to a wide variety of aryl fluorides with a C(sp2)-F bond. This method can be extended to other coupling partners with a C(sp3)-H bond, including diarylmethanes, diarylethanes, and monoarylalkanes. Many di- and triarylalkanes with tertiary or quaternary carbon centers can be obtained easily in moderate to high yields. We believe that the developed silylboronate-mediated cross-coupling method is a valuable contribution to C-F and C-H activation chemistry.

Etherification of Fluoroarenes with Alkoxyboronic Acid Pinacol Esters via C-F Bond Cleavage.

Potassium-base-mediated defluoroetherification of aryl and heteroaryl fluorides with alkoxyboronic acid pinacol esters under transition-metal-free conditions is reported. This protocol efficiently and safely provides a wide variety of aryl ethers in high yields without using metal catalysts, specific ligands, and harsh conditions to selectively forge Csp2-O bonds via the Csp2-F cleavage. This method can be applied to the late-stage etherification of structurally complex Csp2-fluorides and bioactive alcohols, such as ß-estradiol, calciferol, and tocopherol.

Catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation.

A regioselective carbosilylation of alkenes has emerged as a powerful strategy to access molecules with functionalized silylated alkanes, by incorporating silyl and carbon groups across an alkene double bond. However, to the best of our knowledge, organic fluorides have never been used in this protocol. Here we disclose the catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides mediated by tBuOK. The main feature of this transformation is the selective activation of the C-F bond of an organic fluoride by the silyl boronate without undergoing potential side-reactions involving C-O, C-Cl, heteroaryl-CH, and even CF3 groups. Various silylated alkanes with tertiary or quaternary carbon centers that have aromatic, hetero-aromatic, and/or aliphatic groups at the ß-position are synthesized in a single step from substituted or non-substituted aryl alkenes. An intramolecular variant of this carbosilylation is also achieved via the reaction of a fluoroarene with a ω-alkenyl side chain and a silyl boronate.

Two Catalytic Annulation Modes via Cu-Allenylidenes with Sulfur Ylides that Are Dominated by the Presence or Absence of Trifluoromethyl Substituents.

We disclose the Cu-catalyzed enantioselective synthesis of 3-methyl-3-propargyl-indolines, which contain a quaternary stereogenic carbon center, via the decarboxylative [4 + 1] annulation of 4-methyl-4-propargyl-benzoxazinanones with variety of sulfur ylides. The reaction proceeds predominantly through a γ-attack at the Cu-allenylidene intermediates by sulfur ylides to provide the corresponding indolines in good yield and high enantioselectivity (up to 91% ee). In contrast, the reaction of 4-trifluoromethyl-4-propargyl-benzoxazinanones with sulfur ylides delivers 3-trifluoromethyl-2-functionalized indoles in good to high yield via an unexpected α-attack at the Cu-allenylidene intermediates. Control over the α/γ-attack at the Cu-allenylidene intermediates by the same interceptors was achieved for the first time by the use of trifluoromethyl substituents.