Further studies on the amine directed hydrocarboxylation are presented. Hydrocarboxylation of (N-(2-butyl-3,3-dideutero)-4-pentenyl-n-butylamine) carbonyl rhodium chloride gave rise to 1-butyl-3-methyl-4,4-dideutero-5-butyl-2-piperidinone exclusively in 71% yield with no evidence of deuterium scrambling. This result strongly suggests that the hydrocarboxylation does not proceed through a $\pi$-allyl rhodium complex. The diastereoselectivity of the formation of Rh(I) complexes was influenced by alkene geometry, amine substituents and a chiral group on nitrogen. Steric interactions in the Rh(I) complexes account for the diastereofacial selectivity of the coordination of the alkene to the rhodium. / Investigations were performed on approaches to the stereoselective synthesis of corynantheidol. Studies towards the preparation of cis 3,4-disubstituted piperidinone key intermediates indicated that reaction of cis bishomoallylic amines with (Rh(CO)$\sb2$Cl) $\sb2$ or (Rh(CO)(ethylene)Cl) $\sb2$ did not give rise to Rh(I) complexes and oxygen functionalities in the olefin amines hindered the hydrocarboxylation of Rh(I) complexes. Cis-3-ethyl-4-(3-methyl-2-butenyl)-2-piperidinone which was a suitable key intermediate for synthesis of corynantheidol was obtained with high diastereoselectivity, but in modest yield. Attempts to hydrocarboxylate of Rh(I) complexes with a number of ligands on nitrogen are also described. / Source: Dissertation Abstracts International, Volume: 55-04, Section: B, page: 1445. / Major Professor: Marie E. Krafft. / Thesis (Ph.D.)--The Florida State University, 1994.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77178 |
| Contributors | Yu, Xiang Yang., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 373 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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