Magnesium iodide etherate

Magnesium iodide etherate, MgE-OiC.H,), (1). The reagent is prepared by reaction of Mg(0) and 1, in benzene-ether. 

Similar to (chloromethyl)trimethylsilane, (chloromethyl)di-methylphenylsilane can be used to prepare alkenes via a Peterson olefination by treating C=0 compounds with Grignard 29. However, due to its propensity for rearrangements under the conditions needed for the elimination step, 1 appears less suited for this task than (chloromethyl)trimethylsilane if the silyl terminal alkenes are desired. However, in a parallel transformation, it was found that if the )3-silylalcohol 31 is treated with magnesium iodide etherate, then the Julia ring-opened homoallylation adduct 32 could be isolated (eq 15). ... 

Magnesium iodide is soluble in alcohols and many other organic solvents, and forms numerous addition compounds with alcohols, ethers, aldehydes, esters, and amines. One example is magnesium iodide dietherate [29964-67-8], Mgl2 prepared by gradual addition of iodine to a... 

Epoxide (88) is converted to C-norpregnane (89) in 60% yield by methyl-magnesium iodide in refluxing ether-benzene. No rearrangement to the C-norsteroid occurs with dimethylmagnesium. 

Oddo reported over 50 years ago that the interaction of methyl iodide with indole magnesium iodide at the reflux temperature of ether for 12 hours produced 3-methylindole (2). Rather surprisingly,... 

Bruce and Sutcliffe obtained l-acetyl-2-methyl-3-phenylindole (123) by the action of acetyl chloride on 2-methyl-3-pheiiylindole magnesium iodide in ether.These authors were able to obtain l-benzoyl-2-benzyl-3-phenylindole (124) but not l-acetyl-2-benzyl-3-phenylindole (125) from 2-benzyl-3-phenylindole magnesium iodide by analogous procedures.3-Acetyl-2-phenylindole (126) and 3-propionyl-2-pheny]indole (127) have recently been prepared in fair yield by the acylation of 2-phenylindole magnesium iodide with acetyl and propionyl chloride, respectively. Le ete obtained a mixture of l-acetyl-3-ethylindole (128) and 2-acetyl-3-ethylindole (129) by the interaction of acetyl chloride with 3-ethylindole magnesium iodide in ether. 

Kalir and Szara obtained l,3-bis(a-chloropropionyl)indole (140) by the action of a 20% excess of a-chloropropionyl chloride on indole magnesium bromide in an ether-toluene mixture. On the other hand, Ganellin and Ridley obtained 3-(o -chloropropionyl)indole (141) by the action of a 10% excess of a-chloropropionyl chloride on indole magnesium iodide in anisole. -... 

Hi. Isopropylideneglyceroyl chloride. 3-(a,/3-Dihydroxypropionyl)-indole (205) has recently been obtained by hydrolysis of its isopro-pylidene derivative which, in turn, was produced by the action of isopropylideneglyceroyl chloride (206) on indole magnesium iodide in ether. 

In 1922 Majima and Kotake reported that 3-formylindole (209) could be obtained in yields of up to 40% by the action of a fivefold excess of ethyl formate on indole magnesium iodide in anisole at low temperatures. However, they also claimed that only traces of the aldehyde were obtained when the reaction was carried out in ether. ... 

Acetylindole (213) was obtained by the action of ethyl acetate on indole magnesium iodide at low temperatures slightly higher yields were obtained when the reaction was carried out in anisole rather than in ether. Putochin subsequently observed that when the reaction was carried out in benzene at 85° both 213 and 3-acetylindole (109)... 

Dimethylindole magnesium iodide reacts with chloroacetonitrile in ether to give 3-cyanomethyl-2,3-dimethylindolenine (234). Majima and Hoshino obtained 3-(2-cyanoethyl)lndole (235) by the action of -chloropropionitrile on indole magnesium iodide. The reaction was slower with -chloropropionitrilc than with chloro-aoetonitrile. 3-(3-Cyano-w-propyl)indole (236), required as an intermediate in the synthesis of 3-indolyl-y-w-butyric acid, was prepared, but not isolated, by the action of y-chloro-w-butyronitrile on indole magnesium iodide. ... 

Zenitz obtained the analogous compounds 237 and 238 by the action of the corresponding a-cyano-w-bromo-w-alkanes on 2-methylindolyl magnesium bromide in ether. Eiter and Svierak prepared a-(3-indolyl)propionitrile (239) by the action of a-bromopropionitrile on indole magnesium iodide in anisole. ... 

Majima et al. prepared ethyl y-(3-indolyl)-y-oxobut3rrate (250) in a similar manner by the condensation of the indole Grignard reagent with -ethoxycarboiiylpropionyl chloride.Methyl y-(3-indolyl)-y-oxobutyrate (251) has been obtained by the action of mcthoxycarbonylpropionyl chloride on indole magnesium iodide in ether. Ballantine et al. prepared methyl y-(5-methoxy-3-... 

In 1956 Ames et al. reported that a low yield of l-benzamido-2,2-di-(3-indolyl)ethane (316) was obtained in an attempt to prepare 3-(2-benzamido-l-hydroxyethyl)indole (317) by the action of hcnzamido-acetaldehyde on indole magnesium iodide in ether. 

Indolyl-3 -isoquinolylmethanol (333) (22%) and a small quantity of an unidentified by-product were formed by the action of 3-iso-quinolinecarboxaldehyde on indole magnesium iodide in ether-methylene chloride at room temperature. The expected methanol... 

Indole magnesium iodide reacts with nitroethylene to give 3-(2-nitroethyl)indole (351) in good yield (Noland and Hartman ). Noland et al. subsequently showed that this reaction, which is usually carried out in ether at 0°, was of general applicability and reported... 

Aza-3,4-benzo-5,6-dipropylpentatriafu]valene hydriodide (373) was obtained in 20% yield by the action of l,2-di-n-propyl-3-ethoxy-cyclopropenium fluoroborate on indole magnesium iodide in a methylene chloride-ether mixture. 

Oddo and Sessa claimed that 1-carboxyindole (375) was obtained on treatment of indole magnesium iodide with gaseous carbon dioxide. Majima and Kotake later reported that 3-carboxyindole (376) and not 375 was the main product obtained in this reaction improved yields of 376 were obtained when the reaction was carried out in anisole instead of ether.Subsequently, several workers have employed essentially this procedure, for the synthesis of 376. It has recently been shown, however, that both the acids 375 and 376 are formed in approximately equal amounts by the carbonation of the indole Grignard reagent (Kasparek and Hea-cook ). 

Jardine and Brown reported that the product obtained on treatment of indole magnesium iodide in ether with deuterium oxide in tetrahydrofuran was deuterated to the extent of about 50% in both the 1- and 3-positions of the indole nucleus. ... 

To an ethereal solution of methyl magnesium iodide prepared from 26.7 g (1.1 mols) of magnesium and 160 g (1.13 mols) Of methyl iodide in 200 cc of dry ether, is added a solution of 79 g (0.72 mol) of cyclopentylacetonitrile in 100 cc of dry ether. The reaction mixture is refluxed for 4 hours. The reaction mixture is then decomposed with ice in the usual way, and the ether layer containing the cyclopentylacetone is separated, is dried over anhydrous magnesium sulfate and the ether removed by evaporation. The residue comprising cyclopentylacetone is purified by distillation in vacuo. The cyclopentylacetone boils at 82° to 84°C at about 32 mm pressure. 

The reaction of isopropylidene piperidinomethylenemalonate and methyl magnesium iodide in a mixture of diethyl ether and THF at room temperature gave isopropylidene ethylidenemalonate in 92% yield (88JA1880) (Scheme 58). 

The copper-catalyzed conjugate addition of methyl magnesium iodide to cyclohexenone and trapping the enolate as its trimethylsilyl enol ether, followed by a trityl hexachloro-antinomate-catalyzed Mukaiyama reaction, is apphed to / -(—jcarvone. C-2, C-3 functionalized chiral cyclohexanones are converted into their a-cyano ketones, which are submitted to Robinson annulation with methyl vinyl ketone. Highly functionalized chiral decalones are obtained that can be used as starting compounds in the total synthesis of enantiomerically pure clerodanes (equation 70). 

Was prepd by treating acetylene-bis-magnesium iodide, Mgl.CiC.Mg I, in ether with arsenium trichloride... 

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