One-Pot Synthesis of Indolin-3-ones Mediated by LiN(SiMe3)2/CsF.

Indolin-3-ones are essential heterocycles with wide-ranging biological activities and medicinal values, and therefore, efficient approaches to their synthesis remain in demand. Herein, a novel and operationally simple method to generate indolin-3-ones is reported by using a tandem reaction of N-methylbenzylamines and methyl 2-fluorobenzoates mediated by the LiN(SiMe3)2 and CsF system (34 examples, 30-85% yields). The synthesis of C2-quaternary indolin-3-one further demonstrated the potential practicability of these tandem reactions.

Discovery of Novel Pyrazole Acyl Thiourea Skeleton Analogue as Potential Herbicide Candidates.

To discover novel transketolase (TKL, EC 2.2.1.1) inhibitors with potential herbicidal applications, a series of pyrazole acyl thiourea derivatives were designed based on a previously obtained pyrazolamide acyl lead compound, employing a scaffold hopping strategy. The compounds were synthesized, their structures were characterized, and they were evaluated for herbicidal activities. The results indicate that 7a exhibited exceptional herbicidal activity against Digitaria sanguinalis and Amaranthus retroflexus at a dosage of 90 g ai/ha, using the foliar spray method in a greenhouse. This performance is comparable to that of commercial products, such as nicosulfuron and mesotrione. Moreover, 7a showed moderate growth inhibitory activity against the young root and stem of A. retroflexus at 200 mg/L in the small cup method, similar to that of nicosulfuron and mesotrione. Subsequent mode-of-action verification experiments revealed that 7a and 7e inhibited Setaria viridis TKL (SvTKL) enzyme activity, with IC50 values of 0.740 and 0.474 mg/L, respectively. Furthermore, they exhibited inhibitory effects on the Brassica napus acetohydroxyacid synthase enzyme activity. Molecular docking predicted potential interactions between these (7a and 7e) and SvTKL. A greenhouse experiment demonstrated that 7a exhibited favorable crop safety at 150 g ai/ha. Therefore, 7a is a promising herbicidal candidate that is worthy of further development.

Synthesis of Homoallylamines Enabled by Cobalt or Palladium Catalyzed Allylic Substitution of Azaarylmethylamines.

Pd(OAc)2/Nixantphos or CoI2/Nixantphos catalyzed allylic substitutions with weakly acidic C(sp)3-H bonds of azaarylmethylamines are described. This method facilitates access to various kinds of heteroaryl rings containing homoallylamines (39 examples, 30-98% yields) with excellent functional group tolerance and diastereoselectivity. Compared with the Pd/Nixantphos complex, the Co/Nixantphos catalysis could obtain the cyclic products with good to excellent diastereoselectivities. Importantly, the CoI2/(R,R)-Me-Duphos catalyzed reactions exhibit moderate enantioselectivity. Additionally, the scalability of this transformation is successfully demonstrated.