Alkaloids from the Roots of Saccopetalum prolificum

In recent years, an increased interest in the phytochemistry of the Annonaceae has beensparked by the isolation of the antileukemic Annonaceous acetogenin'. Saccopela/umprolificllm (Chun el How) Tsiang (Allnonaceae) is an evergreen tree distributed inHainan Province, P. R. China. The ethanolic extract of the plant exhibited cell growthinhibitory activity (20 ig/ml) against LIZ10 lymphocytic leukemia. A new alkaloid,prolifine (l), was isolated from the roots of S. proldicum, in addition t…     

Asymmetric total synthesis of the indole alkaloid cyclopiazonic acid and first structure-activity data

The indole alkaloid α-cyclopiazonic acid (CPA) is one of the few known inhibitors of sarco(endo)plasmic reticulum Ca²⁺-ATPase (SERCA) besides the terpenoids thapsigargin and artemisinin. We report here the first asymmetric total synthesis of cyclopiazonic acid by a modification of the Knight synthesis, currently the most efficient route to CPA. First structure-activity data of CPA derivatives and stereoisomers are presented and will be discussed in connection with the published crystal structures of CPA-SERCA complexes.     

Water and fluorinated alcohol mediated/promoted tandem insertion/aerobic oxidation/bisindolylation under metal-free conditions: Easy access to bis(indolyl)methanes

A green tandem reaction, including insertion/aerobic oxidation/bisindolylation, starting from indoles and diazo compounds has been developed. The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation. Molecular oxygen in the air acts as an oxidant. 3,3′-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions. No any catalyst and additive were required. N₂ and water were released as sole by-products. Absence of water and fluorinated alcohol resulted in Wolff rearrangement product.     

CO_2 Adducts of the Amino and Imino Groups Studied by ~1HNMR and ~(13)CNMR

When isolating 1,4-dideoxy-1,4-imino-D-arabinitol using Dowex 1(2 (OH- form) or CM-Sephadex C-25 (NH4+ form), we found another compound always accompanied with it. It was apparent that the two compounds had similar structures from their 1HNMR and 13CNMR in D2O (Fig. 1). At first, we guessed the two compounds were isomerides. But when acid was added into the solution of the two compounds, the signals for the minor compound disappeared.Figure 1 13CNMR of 1,4-dideoxy-1,4-imino-D-arabin…     

Organocatalyzed enantioselective synthesis of 6-amino-5-cyanodihydropyrano[2,3-c]pyrazoles

The first enantioselective synthesis of biologically active 6-amino-5-cyanodihydropyrano[2,3-c]pyrazoles has been achieved through a cinchona alkaloid-catalyzed tandem Michael addition and Thorpe-Ziegler type reaction between 2-pyrazolin-5-ones and benzylidenemalononitriles. The reaction may also be carried out in a three-component or a four-component fashion via the in situ formation of these two components from simple and readily available starting materials. The desired products were obtained in excellent yields with mediocre to excellent enantioselectivities (up to >99% ee).     

IMPERIAZINE, A NEW ALKALOID FROM Petilium eduardi

The new C-nor-D-homosteroidal alkaloid imperiazine was isolated from the bulbous plantPetilium eduardiRgl. (Liliaceae). The structure was established using spectral data.     

A rapid and highly efficient Michael addition of methoxybenzenes and indoles to α,β-unsaturated ketones using BF3·OEt2 as a catalyst

An efficient and general protocol is described for the Michael addition of α,β-unsaturated ketones with electron-rich arenes/indoles to give alkylated arenes/indoles under mild reaction condition at room temperature. Shorter reaction time, convenient and good isolated yields are the significant features of this protocol. Moreover, the procedure is environmentally benign in nature and applicable to variety of arenes/indoles as well as α,β-unsaturated ketones.     

Controlling Regioselectivity in the Enantioselective N‐Alkylation of Indole Analogues Catalyzed by Dinuclear Zinc‐ProPhenol

The enantioselective N‐alkylation of indole and its derivatives with aldimines is efficiently catalyzed by a zinc‐ProPhenol dinuclear complex under mild conditions to afford N‐alkylated indole derivatives in good yield (up to 86 %) and excellent enantiomeric ratio (up to 99.5:0.5 e.r.). This method tolerates a wide array of indoles, as well as pyrrole and carbazole, to afford the corresponding N‐alkylation products. The reaction can be run on a gram scale with reduced catalyst loading without impacting the efficiency. The chiral aminals were further elaborated into various chiral polyheterocyclic derivatives. The surprising stability of the chiral N‐alkylation products will open new windows for asymmetric catalysis and medicinal chemistry.     

Palladium-Catalyzed Regioselective Synthesis of 3-Arylindoles from N-Ts-Anilines and Styrenes

A Pd-catalyzed intermolecular oxidative annulation between N-Ts-anilines and styrenes was developed. This method offers a straightforward and robust approach to a wide range of 3-arylindoles using readily available starting materials with good functional-group tolerance and high regioselectivity and efficiency. Further elaboration of the products obtained from this process provided access to highly functionalized and structurally diverse indoles, for example, 3-(indol-3-yl)carbazoles, 1,9-dihydropyrrolo-[2,3-b]carbazoles, and 3′-aryl-3,5′-biindoles.