By Howard Alper
Transition steel Organometallics in natural Synthesis: quantity I reports the literature within the box of natural synthesis with a spotlight at the optimal artificial transformations.
The textual content covers subject matters similar to the overall concerns in natural synthesis, C-C and C-X bond formations, and the isomerization and reorganization reactions of olefins. additionally coated are subject matters equivalent to displacement reactions with transition steel complexes, electrophilic reactions of organopalladium complexes, carbonylation reactions, and metal-carbene complexes — its constitution, spectra, bonding, and direct synthesis.
The publication is usually recommended as a reference for chemists and inorganic chemists who want to examine the purposes of organometallic complexes as reagents and catalysts.
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Additional info for Transition Metal Organometallics in Organic Synthesis: v. 1
Example text
CN (94) (95%) (1) R h C I 3, M e O C H 2C H 2O H , (2) N a C N Δ ' (95) PPh2 Mechanisms illustrating the possible types of processes involved in these reactions are suggested for the codimerization reaction [Eq. (87)] and the dimerization reaction [Eq. (90)] (Schemes 6 and 7). 36 ARTHUR J. BIRCH a n d IAN D. JENKINS Scheme 7 IV. C - X B O N D F O R M A T I O N ( X = E L E M E N T O T H E R THAN CARBON) A . Nucleophilic Attack on Coordinated Double Bonds 1. Monoolefins. Wacker Process C - X bond formation by nucleophilic attack on coordinated olefins is in most respects analogous to C - C bond formation (Section IIIA).
145) (Birch and Subba Rao, 1968)], whereas deconjugation is possible in special cases [Eq. (146) (Rinehart and Lasky, 1964)]. ^OMe •Ι π" " ' Ό Me 1 % R h C l ( P P h 3) 3 . C H C 1 3, 2 hr \ \ f l^JJ (145) (80%) Isomerization of conjugated dienes is possible by protonation of the corresponding tricarbonyliron complexes [Eqs. (147) (Birch and Williamson, 1973) and (148) (Birch et ai, 1975)]. These isomerizations presumably also involve transfer of allylic hydrogen to the transition metal (cf. Scheme 11).
In contrast to the 1-carbomethoxydiene system, the corresponding 5-carbomethoxycyclohexa-l,3-diene complex undergoes ARTHUR J. BIRCH a n d IAN D. JENKINS dideuteration to give the 5,6-dideuterio-l-carbomethoxy-l,3-diene complex as predicted by Scheme 11. One example of a stereospecific deuteration on the side of the molecule opposite the tricarbonyliron group has been observed [Eq. , ο ο Scheme 12 1972)]. In this case, the tricarbonyliron group almost certainly facilitates initial protonation on oxygen.