The stems of several Dendrobium species (Orchidaceae) are used in traditional Chinese medicine as a tonic to nourish the stomach, promote the production of body fluid, and reduce fever [1]. The products prepared from the dried stems of Dendrobium plants are also used as precious health foods and nutrients [2]. Earlier work on the genus led to the isolation of a series of compounds such as alkaloids, fluorenones, sesquiterpenoids, bibenzyls, and phenanthrenes with antioxidant, antitumor, antimutagenic, and other activities [3][4][5][6]. D. longicornu Lindl is distributed in Nepal, Sikkim, Bhutan, India, Vietnam, and the southwestern part of China [7]. Previously, there have been no reports on its chemical constituents. In the course of our search for new bioactive natural products from medicinal plants in Yunnan of China, we investigated the plant.D. longicornu was collected from Lianghe County of Yunnan Province, China in September, 2004. The air-dried whole plants (3.4 kg) were chopped and extracted with 95% EtOH five times (each 20 L) at room temperature. The EtOH extract (115 g) was diluted with H 2 O (1 L) and then extracted with petroleum ether, EtOAc, and n-BuOH (each 0.5 L, five times) successively. Evaporation of the respective solvents gave the petroleum ether (30 g), EtOAc (26 g), and n-BuOH (52 g) extracts.The EtOAc extract (26 g) was applied to a silica gel column (200-300 mesh, 100 cm × 10 cm), eluting with petroleum ether containing increasing amounts of acetone to obtain six fractions monitored by TLC tests. Spots on the plate were observed under UV light and visualized by spraying with 15% H 2 SO 4 in ethanol followed by heating. Fraction 1 (2 g) was further purified on column chromatography (silica gel, 200-300 mesh, 60 cm × 4 cm, petroleum ether-acetone 30:1) to afford five subfractions. The second and third subfractions were isolated on preparative TLC (20 cm × 20 cm, petroleum ether-benzene 1:1) to afford 1 (40 mg) and 2 (35 mg), respectively. The fourth subfraction was purified by recrystallization from acetone to obtain 8 (100 mg); Fr. 2 (4.5 g) was separated on column chromatography (silica gel, 200-300 mesh, 60 cm × 5 cm, CHCl 3 -acetone 15:1) to yield five subfractions. The second subfraction was isolated on a Sephadex LH-20 column (120 cm × 3 cm, MeOH) to obtain 5 (15 mg). The third subfraction was purified on a preparative TLC plate (20 cm × 20 cm, petroleum etherEtOAc 9:1) to afford 7 (8 mg). The fourth subfraction was separated on a preparative TLC plate (20 cm × 20 cm, CHCl 3 -acetone 15:1) to afford 6 (6 mg); Fr. 5 (9 g) was purified on column chromatography (silica gel, 200-300 mesh, 60 cm × 4 cm, CHCl 3 -acetone 10:1) to afford two subfractions. The second subfraction (3 g) was subjected to repeated column chromatography similarly, first on Sephadex LH-20 (MeOH), and then on preparative TLC (20 cm × 20 cm, petroleum etherEtOAc 2:1, CHCl 3 -MeOH 15:1) to isolate 3 (11 mg) and 4 (20 mg). OR O OR O 1, 2 1: R = CH 2 CH(C 2 H 5 )(CH 2 ) 3 CH 3 2: R = (CH 2 ) 3 CH 3 CHO OH HO CH 3 COOC ...