The Pd-catalyzed direct C(sp2)–H arylation of aromatic ketones using a transient directing group is described. The ketimine/carboxylate bidentate directing group in situ generated from aromatic ketone and glycine enabled a palladium-catalyzed ortho-C–H arylation, which shows extensive substrate compatibility.

A series of (2-benzoylethen-1-ol)-containing benzothiazine derivatives was synthesized, and their herbicidal activities were first evaluated. The bioassay results indicated that some of 3-benzoyl-4-hydroxy-2-methyl-2H-1,2-benzothiazine-1,1-dioxide derivatives displayed good herbicidal activity in greenhouse testing, especially, compound 4w had good pre-emergent herbicidal activities against Brassica campestris, Amaranthus retroflexus and Echinochloa crusgalli even at a dosage of 187.5 g ha−1. More importantly, compound 4w displayed significant inhibitory activity against Arabidopsis thaliana HPPD and was identified as the most potent candidate with IC50 value of 0.48 μM, which is better than the commercial herbicide sulctrione (IC50 = 0.53 μM) and comparable with the commercial herbicide mesotrione (IC50 = 0.25 μM). The structure–activity relationships was studied and provided some useful information for improving herbicidal activity. The present work indicated that (2-benzoylethen-1-ol)-containing 1,2-benzothiazine motif could be a potential lead structure for further development of novel HPPD inhibiting-based herbicides.

An efficient synthesis of dihydrobenzo[c]phenanthridinones was achieved by utilizing an indium(0)-mediated intramolecular cyclization reaction under ligand- and base-free conditions. A variety of functional groups were tolerated in the present protocol.

A highly efficient asymmetric hydrogenation of cyclic imines containing a pyridyl moiety was established by using iridium catalysts with chiral spiro phosphine-oxazoline ligands. This process will facilitate the development of new nicotine-related pharmaceuticals. The introduction of a substituent at the ortho position of the pyridyl ring to reduce its coordinating ability ensures the success of the hydrogenation and excellent enantioselectivity.

The stereochemical course of indium-promoted allylations to α-chiral aldehydes with 3-bromomethyl-5H-furan-2-one was investigated in anhydrous THF and pure H2O. High levels of 3,4-syn;4,5-syn diastereomers were produced with free hydroxyl derivatives whether in THF or pure H2O, reflecting the promising synthetic potential of this chemistry. This stereo-differentiation was attributed to the strong geometric bias exercised by our allylindium reagent and adherence to a chelation control transition-state alignment. Meanwhile, heightened levels of 3,4-anti;4,5-anti diastereomers were obtained with the rigid aldehydes 1h and 1i.

An efficient and diastereoselective Pd-catalyzed method of allylation of aldehydes with 3-bromomethyl-5H-furan-2-one is described. The proposed method allows the synthesis of β-(hydroxymethylaryl/alkyl)-α-methylene-γ-butyrolactones with a syn relative configuration for the first time.

The annulation reaction of methyl o-halobenzoates with azabicyclic alkenes proceeds efficiently to give the corresponding benzo[c]phenanthridine derivatives in good to excellent yields using a developed base-free methodology based on our preliminary studies. Thirty-seven application examples validate the compatibility of the present strategy with different groups, particularly with the electron-deficient ones, that are difficult to access using other traditional methods. In addition, annulation reactions with non-symmetric azabicyclic alkenes are achieved in high regioselectivity.

A zinc or indium-mediated Barbier-type allylation of aldehydes with 3-bromomethyl-5H-furan-2-one in aqueous solvents was developed to provide an efficient route to α-methylene-γ-butyrolactone, which is synthetically very useful. The desired products were obtained in moderate to high yields in aqueous solvents. Excellent drs were achieved, among which the best diastereomeric ratios of products were found when water was used in the indium-mediated reaction, and THF–NH4Cl (sat, aq) (2:1) mixture in the zinc-mediated reaction. Furthermore, the allylation can be induced by chiral centers, especially those in the α-position, as a substrate-controlled reaction to obtain the enantioselective homoallylation alcohols.

A highly efficient route was developed to synthesize (−)-8-epigrosheimin in four steps from aldehyde 2 based on a substrate-controlled method. The key steps of the synthesis included (1) a stereo- and regioselective allylation addition, (2) an intramolecular translactonization, and (3) an aldehyde-ene cyclization.

A concise and efficient synthesis of benzo[c]phenanthridines was accomplished by the palladium-catalyzed ring-opening coupling of azabicyclic alkene with o-iodobenzoates, followed by tandem cyclization. The strategy was successfully applied in the total synthesis of benzo[c]phenanthridine alkaloids such as sanguinarine, chelerythrine, nitidine and avicine.

The synthesis of racemic cedarmycin B, an antibiotic from Streptomyces sp. TP-A0456 was achieved firstly from γ-butyrolactone. The key step was a Barbier-type addition of 3-bromomethyl-5H-furan-2-one to formaldehyde mediated by zinc, which afforded the sole γ-addition product 4-hydroxymethyl-3-methylene-dihydrofuran-2-one. The final compound was confirmed by 1H NMR, 13C NMR and HRMS.

The new synthesis of 10-bromo-α-chamigrene was achieved as follows; 6-methyl-5-heptene-2-one was transformed into corresponding thioacetals, and then successively treated with Cp2Ti(P(OEt)3)2. The intermediate reacted with mono-ketal of cyclohexane-1,4-dione, and gave the carbonyl coupling product. It was then transformed into the key intermediate γ-bisabolene via deketalization, Grignard reaction, dehydration and then furnished the target molecule by polyene cyclization, with total yield 2%. All structures were confirmed by 1H NMR and 13C NMR. The final compound was confirmed by 1H NMR, 13C NMR and MS.

The bacillamide 1 is a new algaecide from the marine bacterium Bacillus sp. SY-1. Its analogues bacillamide 3 and alkaloid 4 were firstly synthesized effectively from d-alanine. The key step was a coupling reaction via the mixed anhydride. All structures were confirmed by 1H NMR and 13C NMR. The final compounds were confirmed by 1H NMR, 13C NMR and HRMS and the results are consistent with the reported natural products.

An efficient and diastereoselective Pd-catalyzed method of allylation of aldehydes with 3-bromomethyl-5H-furan-2-one is described. The proposed method allows the synthesis of β-(hydroxymethylaryl/alkyl)-α-methylene-γ-butyrolactones with a syn relative configuration for the first time.

A zinc or indium-mediated Barbier-type allylation of aldehydes with 3-bromomethyl-5H-furan-2-one in aqueous solvents was developed to provide an efficient route to α-methylene-γ-butyrolactone, which is synthetically very useful. The desired products were obtained in moderate to high yields in aqueous solvents. Excellent drs were achieved, among which the best diastereomeric ratios of products were found when water was used in the indium-mediated reaction, and THF–NH4Cl (sat, aq) (2:1) mixture in the zinc-mediated reaction. Furthermore, the allylation can be induced by chiral centers, especially those in the α-position, as a substrate-controlled reaction to obtain the enantioselective homoallylation alcohols.

A concise and efficient synthesis of benzo[c]phenanthridines was accomplished by the palladium-catalyzed ring-opening coupling of azabicyclic alkene with o-iodobenzoates, followed by tandem cyclization. The strategy was successfully applied in the total synthesis of benzo[c]phenanthridine alkaloids such as sanguinarine, chelerythrine, nitidine and avicine.