Various attempts were made to enlarge the scope of the common synthetic method for ergot alkaloids illustrated in Chart 1. I. The first total synthesis of (±)-chanoclavine-II (8) was achieved. Thus, epimerization at the C-4 position of the compound (7) afforded the corresponding 4,5-cis compound (10). A series of reactions according to the common synthetic method successfully converted 10 to 8. II. 2-Methoxymethyl-3-buten-2-ol, 2,5-trans-2-phenyl-5-vinyl-1,3-dioxan-5-ol, and optically active (R)-p-tolylvinylsulfoxide were examined as an olefin component in the second step of the common synthetic method. Cyclization of optically active 34 and 35 produced possible four optically active nitrosulfoxides (36; I, II, III, and IV) as shown in Table I. Major products, I and II, were established to be epimers at the C-4 configuration and therefore the reaction was found to proceed in 64% diastereoisomer excess. Establishment of absolute configurations of above stereoisomers is in progress. III. A new coupling reaction for unsymmetrical biaryls was elaborated and was designated as boronation-thallation method. It consists of the reaction of aryl thallium compounds with boronic acids in the presence of a catalytic amount of palladium salt and it tolerates to air and moisture. Applying this new reaction, direct introduction of aromatic and heteroaromatic compound into the 4-position of indole nucleus is realized. Photoreaction of 4-halogenoindoles was also proved to be a useful method for preparing 4-substituted indoles. A novel synthetic method for 4-(3-pyridyl)-3-indolecarbaldehyde (42) from 51 is also reported.