Alkaloids with cyclobutane partial structure are rare. A CAS on-line search resulted in bis(2-methoxycarbonyl-tropyl) α-truxillate from leaves of Erythroxylum coca and santiaguine (diamide from truxillic acid and 1,2,3,4-tetrahydro-5-(2-piperidyl)pyridine). From Schizanthus grahamii (Solanaceae, native to Chile), a new tropane alkaloid grahamine containing a 2-methyl-4-phenylcyclobutane-1,2,3-tricarboxylic triester as the central partial structure was isolated. The dried aboveground parts were extracted, subjected to countercurrent distribution (dichloromethane/McIlvaine buffer, pH=5.4), and column chromatography (alumina 60/E, petroleum ether (40-60°C):ethyl acetate=4:5) to obtain grahamine as an oily, pure, stable substance ([α]D²⁰=+6.21° (c=0.0016 M in CHCl₃), Rf=0.1125). FAB mass spectrometry gave a molecular mass of 871. ¹³C-NMR (46 signals, two with double intensity for monosubstituted benzene) and DEPT subspectra revealed 48 C atoms (7 methyl, 9 methylene, 22 methine, 10 quaternary), leading to the empirical formula C₄₈H₇₂N₃O₁₂ (20 double-bond equivalents). Structure elucidation using 1D and 2D NMR (COSY, DEPT, COLOC) showed three 3,6-dihydroxytropane rings (A, B, C), mesaconic diester (D) linking A and B, 2-methyl-4-phenylcyclobutane-1,2,3-tricarboxylic ester (E) linked to C's 3-hydroxyl group, and angelic ester (F) linked to C's 6-hydroxyl group. Relative configuration of O-acyl groups on tropane rings was derived from HH coupling constants: 3-H pseudo-equatorial (3-O-acyl pseudo-axial); 6-H endo (6-O-acyl exo). The cyclobutane ring presumably forms via [2+2] cycloaddition of mesaconic diester and cinnamic ester. Additionally, the enzyme-catalyzed addition of hydrogen cyanide to aldehydes yields optically active cyanohydrins, a route to chiral β-amino alcohols, α-hydroxy acids, and pyrethroids. High optical purity is challenging due to nonselective chemical addition. While (R)-cyanohydrins synthesis is documented (e.g., Prunus amygdalus oxynitrilase), (S)-cyanohydrins enzymatic synthesis was unstudied. We found that Sorghum bicolor oxynitrilase (4.1.2.11), previously studied botanically in the 1960s, enables preparative synthesis of (S)-cyanohydrins with high optical purity.