Gilman reaction

Hence this chapter provides analogy between silylene and carbene chemistry as a useful approach for construction of small-ring monosilacycles. Furthermore, intramolecular Wurtz, Diyne coupling, Kipping and Gilman reactions have been shown to be useful tools for construction of medium-ring oligosilacycles. 

A related and useful process is the Wittig-Gilman reaction, in which an organolithium (R —Li) reacts with an alkyl halide to produce a new organolithium (R—Li) via metal-halogen exchange.222 Several mechanisms... 

Table 2.1 lists some of the mechanistic studies of organic and organometallic reactions reported in the literature by ESI-MS. All sorts of reactions have been successfully explored in the gas phase, such as the Baylis-Hillman reaction [211-213], C-H or N-H activation [214—219], cydopropanation reaction [220], Diels-Alder reactions [221], displacement reactions [222], electrophilic fluorination [223, 224], Fischer indole synthesis [225], Gilman reaction [226, 227], Grubbs metathesis reaction [228-231], Heck reaction [194], methylenation [232], oxidation [233, 234], Petasis olefination reaction [235], Raney Nickel-catalyzed coupling [236], ruthenium... 

Gilman reaction dimethyl cuprate undergoes C-C bond coupling with methyliodide in the Gas Phase the preferred mechanism for Cu involves the formation of a T-shaped Cu transition state. Heck reaction key ionic intermediates of the Heck reaction of arene diazonium salts were intercepted and structurally characterized. Baylis-Hillman reaction protonated intermediates in the catalytic cyde of the Baylis-Hillman reaction between an activated alkene and an electrophile were intercepted and characterized, providing dired evidence for the currently accepted mechanism. 

V. RING FORMATION BY KIPPING AND GILMAN REACTIONS A. frans-Trisilacycloheptene and [3.1.1]Trisilapropellane... 

Oxidative Addition and Reductive Elimination in the Gilman Reaction... 

The halogen-metal exchange reaction was pioneered by Gilman and co-... 

In addition to those methods already discussed, ketones can also be prepared from certain carboxylic acid derivatives, just as aldehydes can. Among the most useful reactions of this type is that between an acid chloride and a Gilman diorganocopper reagent such as we saw in Section 10.8. We ll discuss this subject in more detail in Section 21.4. 

Coniine, molecular model of. 28 structure of, 294 Conjugate acid, 49 Conjugate base, 49 Conjugate carbonyl addition reaction, 725-729 amines and, 727 enamines and, 897-898 Gilman reagents and, 728-729 mechanism of, 725-726 Michael reactions and, 894-895 water and. 727 Conjugated diene, 482... 

The hydrolysis of the reaction mixture and subsequent separation of the acid is the procedure given by Gilman and Parker (Org. Syn. 5, 25). Sulfuric acid should be added during the hydrolysis as long as any particles of magnesium are present. The water layer does not become clear, due to solidification of the organic acid. 

Since the preformed aggregate Bu3Cu2Li showed a diastereoselectivity of 83 17 in the presence of boron trifluoride16, the low diastereoselectivity noted above was presumably due to a faster addition reaction of butyllithium, which is formed by the treatment of the Gilman cuprate with the boron trifluoride-diethyl ether complex16,, s. 

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