Relative Reactivities of Organometallic Compounds. XX.^* Metalation

Abstract

of Some Organic Compounds 109 was added equivalent amounts of anisóle and p-bromoanisole. The mixture was then concentrated to 55 cc., refluxed for twenty hours, and carbonated to yield 30% of 5-bromo-2-methoxybenzoic acid. From a related experiment in which the ether solution was not concentrated, there was isolated a mixture of 5-bromo-2-methoxybenzoic acid and ^-methoxybenzoic acid.

Totalsynthese von Nosiheptid

“…[234] Schema 4.2: Darstellung chiraler 1,4-Diole durch Epoxid-Hydrosilylierung nach Gansäuer et al. [234] Die durch Gilman [235] und Wittig [236] unabhängig voneinander entdeckte ortho-Metallierung von Aromaten stellt ein weiteres Beispiel für eine wichtige substratdirigierte Reaktion dar. [237][238][239] Die Gruppe von Uchiyama konnte zeigen, dass durch dirigierte ortho-Cuprierung eine direkte Hydroxylierung sowie Aminierung von Aromaten möglich ist (Schema 4.3).…”

Organosodium and Organopotassium Compounds Part I: Properties and Reactions

“…Anisole [56,70], diphenyl ether [78], and diphenyl sulfide [70] are metalated in the ortho-position. With methyl phenyl sulfide, the side chain is more reactive because the d-orbitals of the sulfur participate in the resonance (43) [79].…”

“…e. it is metalated by strong organometallic compounds in one of the two orthopositions [70]. The orfho-positions in dibenzofuran are far more activated.…”

“…This compound is attacked even by methyl-lithium, and benzylsodium, a relatively weak base, converts it into the o,o'-disodio derivative in 80 % yield [80]. Aniline [81] and its derivatives [56,70,82] are also metalated in the ortho-position [e.g. (44)].…”

“…The reactions dealt with in the following all have the common feature that the organoalkali compound adds onto an electron-deficiency site (69) or across a multiple bond (70).…”