Dienediamine: A safe surrogate for the herbicide paraquat.

Paraquat (PQ) has been used as an herbicide worldwide because of its potent activity against weeds. However, it is highly toxic to humans. The very high fatality of PQ poisoning is due to its inherent toxicity and the lack of any effective treatment. Consequently, developing a non-toxic herbicide with comparable efficacy to PQ will contribute to global food security and help prevent PQ-related fatalities. Herein, we report a new herbicide called dienediamine, which was discovered from how to intervene the redox cycle of PQ, an inherent toxicity nature. Dienediamine, the "reduced" form of PQ with no function as an electron transfer agent, was shown to be non-toxic through comprehensive in vivo and in vitro experiments at molar concentrations equivalent to PQ's absolute lethal dose. Remarkably, dienediamine can undergo conversion to PQ under natural sunlight and ambient air conditions, exhibiting herbicidal activities that are comparable to those of PQ. The conversion of dienediamine to PQ, which is toxic to chloroplasts, is the key mechanism underlying its potent herbicidal activity. Our study discovers that dienediamine is a safe and superior alternative to PQ, possessing significant potential for application in sustainable agriculture globally.

Metal-free reduction of unsaturated carbonyls, quinones, and pyridinium salts with tetrahydroxydiboron/water.

A series of unsaturated carbonyls, quinones, and pyridinium salts have been effectively reduced to the corresponding saturated carbonyls, dihydroxybenzenes, and hydropyridines in moderate to high yields with tetrahydroxydiboron/water as a mild, convenient, and metal-free reduction system. Deuterium-labeling experiments have revealed this protocol to be an exclusive transfer hydrogenation process from water.

Construction of Various Bridged Polycyclic Skeletons by Palladium-Catalyzed Dearomatization.

A powerful palladium-catalyzed dearomative cyclization was developed that provides facile access to eight types of bridged tetracyclic skeletons bearing various ring sizes and heterocycles. With this method, several skeletons or analogues of natural products, including tubingensin B and dracaenones, were synthesized. Asymmetric dearomative cyclization enables the construction of various enantiomerically enriched bridged polycyclic systems with up to 99 % ee by employing a chiral palladium catalyst.

Stereoelectronic Effects in Ligand Design: Enantioselective Rhodium-Catalyzed Hydrogenation of Aliphatic Cyclic Tetrasubstituted Enamides and Concise Synthesis of (R)-Tofacitinib.

We herein report the development of a conformationally defined, electron-rich, C2 -symmetric, P-chiral bisphosphorus ligand, ArcPhos, by taking advantage of stereoelectronic effects in ligand design. With the Rh-ArcPhos catalyst, excellent enantioselectivities and unprecedentedly high turnovers (TON up to 10 000) were achieved in the asymmetric hydrogenation of aliphatic carbocyclic and heterocyclic tetrasubstituted enamides, to generate a series of chiral cis-2-alkyl-substituted carbocyclic and heterocyclic amine derivatives in excellent enantiomeric ratios. This method also enabled an efficient and practical synthesis of the Janus kinase inhibitor (R)-tofacitinib.

Stereospecific Nucleophilic Substitution with Arylboronic Acids as Nucleophiles in the Presence of a CONH Group.

Stereospecific nucleophilic substitution was achieved for the first time with arylboronic acids as nucleophiles. This transition-metal-free coupling between chiral α-aryl-α-mesylated acetamides and arylboronic acids provided access to a series of chiral α,α-diaryl acetamides with excellent enantioselectivity and moderate to good yields. The CONH functionality proved to be crucial for bridging the reactants and promoting the reaction. Efficient syntheses of a cannabinoid CB1 receptor ligand, the antidepressant (S)-diclofensine, and a key chiral building block of the inhibitor implitapide were successfully accomplished by using this method.

Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles.

We herein report a transition-metal-free cross-coupling between secondary alkyl halides/mesylates and aryl/alkenylboronic acid, providing expedited access to a series of nonchiral/chiral coupling products in moderate to good yields. Stereospecific SN2-type coupling is developed for the first time with alkenylboronic acids as pure nucleophiles, offering an attractive alternative to the stereospecific transition-metal-catalyzed C(sp(2))-C(sp(3)) cross-coupling.