Direct application of benzyl alcohols (or their magnesium salts) as electrophiles in various reactions with Grignard reagents has been developed via transition metal-catalyzed sp(3) C-O bond activation. Ni complex was found to be an efficient catalyst for the first direct cross coupling of benzyl alcohols with aryl/alkyl Grignard reagents, while Fe, Co, or Ni catalysts could promote the unprecedented conversion of benzyl alcohols to benzyl Grignard reagents in the presence of (n)hexylMgCl. These methods offer straightforward pathways to transform benzyl alcohols into a variety of functionalities.

Dibenzopyranones were synthesized by a palladium-catalyzed phenol-directed C-H activation/carbonylation of 2-phenylphenol derivatives in the presence of CO. Pd(OAc)2 was used as a catalyst and Cu(OAc)2 as a catalytic oxidant in the presence of air.

A highly efficient synthesis of planar chiral pyrido[3,4- b] ferrocenes by a palladium-catalyzed enantioselective isocyanide insertion/desymmetric C(sp)-H bond activation reaction was developed. Various planar chiral pyridoferrocenes were obtained in high yields with good to excellent enantioselectivity under mild conditions (up to 99% yield, 99% ee), enabled by a unique SPINOL-derived phosphoramidite ligand.

A Cu-mediated C–H amination for the preparation of primary anilines under redox neutral conditions is developed.

A new instable aristolane type sesquiterpene ketone, gansongone ( 1), was isolated from the fresh underground parts of NARDOSTACHYS CHINESIS Batalin (Valerianaceae), growing in the province Sichuan (China). The structure of 1 was elucidated by spectroscopic and chemical methods. The structure of the corresponding alcohol 2, which was also found in N. CHINENSIS and formerly regarded as 9-aristolene-1alpha-ol ( 5) has to be revised to l(10)-aristolene-9beta-ol ( 2) from results of 2D-NMR-spectroscopy and oxidation to 1. Besides 1 and 2, the following compounds have been identified in the ethanol extract of the fresh plant material of N. CHINENSIS: nardosinone, nardosinondiol, deoxonarchinol A, beta-sitosterol, oleanolic acid, ethyl beta- D-glucopyranoside.

A new strategy for the construction of phenanthridine and isoquinoline scaffolds, starting from arenes containing a pending isocyanide moiety under palladium catalysis, has been developed. This process involves sequential intermolecular isocyanide insertion to an aryl palladium(II) intermediate and intramolecular aromatic C-H activation as key steps. Alkyl palladium(II) intermediate lacking β-hydrogen is also applicable to this reaction, generating unique bisheterocyclic scaffolds with three C-C bonds being formed consecutively.

Two new a-tetralone ( ¼ 3,4-dihydronaphthalen-1(2H)-one) derivatives, berchemiaside A and B (1 and 2, resp.), and one new flavonoid, quercetin-3-O-(2-acetyl-a-l-arabinofuranoside (3), together with ten known flavonoids compounds, eriodictyol (4), aromadendrin (5), trans-dihydroquercetin (6), cisdihydroquercetin (7), kaempferol (8), kaempferol-3-O-a-l-arabinofuranoside (9), quercetin (10), quercetin-3-O-a-l-arabinofuranoside or avicularin (11), quercetin 3'-methyl ether, 3-O-a-l-arabinofuranoside (12), and maesopsin (13), were isolated from the bark of Berchemia floribunda. Their structures were determined by various NMR techniques and chemical studies. Compounds 3 -13 were tested for their cytotoxic activity against human leukemia cells. Among them, kaempferol (8) and maesopsin (13) showed significant inhibitory activities against human leukemia cells CCRF-CEM and its multidrugresistant sub-line, CEM/ADR5000, with IC 50 values of 14.0, 5.3, 10.2, and 12.3 mm, respectively.Introduction. -Berchemia floribunda (Wall.) Brongn., which is widely distributed in China, was used for treatment of rheumatic arthritis, jaundice and contusions, and strains and dysmenorrhoea [1]. No work has been previously performed on the chemical constituents and biological activity. The AcOEt extract showed activity against human leukemia cells CCRF-CEM. So we undertook the study of bioactive constituents. From the AcOEt fraction of EtOH extracts of B. floribunda, two new atetralone ( ¼ 3,4-dihydronaphthalen-1(2H)-one) derivatives, 1 and 2, and one new flavonoid, 3, together with ten known flavonoid compounds, 4 -13, were obtained. Compounds 3 -13 were examined for their biological activities against human leukemia cells CCRF-CEM and its multidrug-resistant sub-line, CEM/ADR5000. This paper mainly reports the isolation and structure elucidation of the new compounds, and the cytotoxicity of the tested compounds.

A general method to construct the scaffolds of dibenzooxazepine and dibenzodiazepine, through Pd-catalyzed isocyanide insertion and intramolecular C(sp 2 )−H activation, has been developed. This is the first example of sevenmembered heterocycle formation by C−H imidoylative annulation.