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.     

Anti-inflammatory chromone alkaloids and glycoside from Dysoxylum binectariferum

Herein we report isolation of a new chromone alkaloid chrotacumine K (12) from fruits and a chromone glycoside schumaniofioside A (13) from leaves of Dysoxylum binectariferum Hook f. Schumaniofioside A is reported for the first time from Meliaceae family. Other known alkaloids isolated include rohitukine (1) and chrotacumine E (6). The structure of new alkaloid 12 was elucidated on the basis of extensive 1D and 2D NMR analysis, synthesis and chemical hydrolysis. Chemically, chrotacumine K (12) is a 3′-O-acetyl rohitukine which on chemical or enzymatic hydrolysis produces rohitukine. The new alkaloid 12 is also present in seeds and stem-barks of this plant. The glycoside schumaniofioside A (13) is present only in leaves, and in abundance (～1% w/w of dried leaves). The isolated compounds and extracts were evaluated for in vitro effect on the proinflammatory cytokines (TNF-α and IL-6) in human monocytic THP-1 cells. The alkaloid 12 displayed potent inhibition (57%) of TNF-α at 0.3 µM, and was non-toxic to THP-1 cells up to 40 µM, indicating its excellent therapeutic window. Furthermore, a nitrobenzoyl ester analog 15e showed better inhibition of IL-6 than parent natural product chrotacumine K.     

Synthetic study of biphenylquinolizidine alkaloids I. Asymmetric total synthesis of lasubine I featuring organocatalyzed asymmetric intramolecular aza-Michael addition

A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition.     

Synthesis and bioactivity of (±)-tetrahydrohaliclonacyclamine A

The total synthesis of tetrahydrohaliclonacyclamine A (5) is described. A key step involves the hydrogenation of an unsaturated bis-piperidine incorporated into a 17-membered macrocycle to provide the cis-syn-cis stereochemistry common to haliclonacyclamines A-D. The hydrogenation product is advanced to the title compound following a five-step reaction sequence. Tetrahydrohaliclonacyclamine A is shown to bind to a variety of ion channels/GPCRs and act as a muscarinic M₁ antagonist.     

Organocatalyzed synthesis of 2-amino-8-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles

2-Amino-8-oxo-tetrahydro-4H-chromene-3-carbonitriles were synthesized for the first time from a tandem Michael addition-cyclization reaction between cyclohexane-1,2-dione and benzylidenemalononitriles. An enantioselective synthesis of these compounds was achieved in moderate ee values (up to 63% ee) by using a cinchona alkaloid-derived thiourea catalyst.     

Trichocarpinine,a Novel Hetidine–Hetisine Type Bisditerpenoid Alkaloid from Aconitum tanguticum var. trichocarpum

Trichocarpinine ( 1 ), the first hetidine–hetisine type bisditerpenoid alkaloid, was isolated from the whole herbs of Aconitum tanguticum var. trichocarpum. Its structure was determined by a combination of spectroscopic techniques, including HR‐ESI‐MS and 1D‐ and 2D‐NMR experiments. Its plausible biogenetic pathway was proposed as well (Scheme).     

Total synthesis of (±)-erythravine based on ring closing dienyne metathesis

The first total synthesis of (±)-erythravine was achieved in thirteen steps from 3,4-dimethoxyphenethylamine using ring closing dienyne metathesis as the key step.     

Studies on the Synthesis of Morphinan Alkaloid： Preparation of the Key Allylic Silyl Ether Precursor

Morphinan alkaloid consisting of many diverse molecules has been attracting much attention of synthetic chemists because of their biologically significant activities and the intriguing structures1. As shown in the common nucleus 1 of these polycyclic frameworks, there is a unique quaternary carbon center with an aryl substituent representing a central synthetic challenge2. In connection with our constant investigations on the quaternary carbon chemistry3, we proposed a general and conceptually…