F Allyl iodide

ACF may also be used for isomerisation of F-olefins [33]. F-Allyl iodide and olefin 79 were readily isomerized under the action of ACF and, as mentioned above, this catalyst is more active in isomerization of F-olefins [23] ... 

The related f-butyl derivative 347 was metallated with w-BuLi and the resulting organo-lithium compound 348 was alkylated with alkyl and allyl iodides, bromides and chlorides in the presence of HMPA519. From 349, several different types of deprotection reactions were possible. Direct hydrolysis to the corresponding aldehydes has been performed under... 

The methods for making allyl alcohol are many. It may be prepared by (a) the action of metals upon dichlorohydrin 1 (b) the reduction of acrolein 2 (c) the action of potassium hydroxide on trimethylene bromide 3 (d) the catalytic decomposition of glycerol with aluminum oxide 4 (e) the hydrolysis of allyl iodide 5 (f) the decomposition of glycerol triformate 6 (g) the action of formic acid upon glycerin 7 and (ft) the action of... 

F. W. Lampe and R. M. Noyes, ihid.y 76, 2140 (1954). Both I2 and allyl iodide, AI, are decomposed by light. Radicals disappear by A -f- O2 AO2 followed by AO2 + I —> products or 2AO2 — products. This differs from the example given. 

Based on these results and results for reduction of other combinations of allyl halides and activated alkenes, it has been suggested that when the allyl halide is more easily reduced than the alkene, the allylic anion (2-F reduction) adds to the activated double bond of the alkene, giving predominantly the terminal alkene [Eq. (32)]. In contrast, initial formation of the radical anion of the (di)activated alkene may lead to an S>j2 reaction between the radical anion and the allyl halide followed by further reduction of the intermediate radical and final protonation [Eq. (33)] [190,191]. However, electron transfer between the alkene radical anion and especially allyl iodide followed by coupling of the allyl radical and a radical anion cannot be ruled out. 

Allyl oxid—Allylic ether—10—98—exists in small quantities in crude essence of garlic. It is obtained as a colorless liquid, having an alliaceous odor insoluble in HuO boiling at 82° (179°.6 F.), by a number of reactions, but best by the action of allyl iodid upon sodium-allyl oxid. 

Allyl iodid—CsH,I—a colorless liquid having a peculiar odor boils at 101 .5 (314 .7 F.) insoluble in HaO obtained by carefully mixing allyl alcohol, red P, and I, and distilling after 24 hours. 

With 41 in hand, a two-step nitro reduction and protection, followed by partial reduction of the lactam and resulting cyclization furnished aminal 42. Further treatment with cyanogen azide generated Wcyanoamidine 43. Hydrolysis and amide protection followed by alkylation with allyl iodide yielded olefin 44 as a single diastereomer. Conversion of 44 to aldehyde 45 was the followed reaction of the mesylate with azide, a cross-aldol reaction with acetone, lactam reprotection with Boc, and trimethylphosphine-mediated reductive rearrangement to provide spiro-y-lactam 46. Methyllithium addition to lactam 46 and similar chemistry as reported by Qin et al. gave communesin F (17) (Scheme 6). 

Benzylic and allylic iodides may readily be coupled in excellent yields under mild conditions via air-induced iodine abstraction using triethylborane as reagent. Mixed coupling. Air passed 45 min. into a mixture of 1 4 benzyl and allyl iodides, and triethylborane in tetrahydrofuran at a rate of 50 ml/min so that the oxygen can be consumed completely by the triethylborane present 4-phenyl-l-butene. Y 72% by GLC. - An excess of the less expensive iodide may be used to increase the conversion to the more valuable material, since the coupling gives a nearly statistical distribution of products. F. e., also prepn. of iodides from boranes, s. A. Suzuki, H. C. Brown et al.. Am. Soc. 95, 1508 (1971). 

The conversion of epoxides to allylic alcohols (Scheme 24) can also be considered here. A variety of reagents, including lithium diethylamide, f-butyldimethylsilyl iodide, a dialkylboryl triflate and an ethylaluminum dialkylamide have been used successfully. 

N-Alkoxylamines 88 are a class of initiators in "living" radical polymerization (Scheme 14). A new methodology for their synthesis mediated by (TMSlsSiH has been developed. The method consists of the trapping of alkyl radicals generated in situ by stable nitroxide radicals. To accomplish this simple reaction sequence, an alkyl bromide or iodide 87 was treated with (TMSlsSiH in the presence of thermally generated f-BuO radicals. The reaction is not a radical chain process and stoichiometric quantities of the radical initiator are required. This method allows the generation of a variety of carbon-centered radicals such as primary, secondary, tertiary, benzylic, allylic, and a-carbonyl, which can be trapped with various nitroxides. 

Diastereoselective syntheses of dihydrobenzo[f>]furans have been accomplished by a rhodium-catalyzed regioselective and enantiospecific intermolecular allylic etherification of o-iodophenols as a key step, providing the corresponding aryl ally ether 122, which leads to a dihydrobenzo[b]furan by treatment of the intermediate aryl iodide with tris(trimethylsilyl)silane and triethylborane at room temperature in the presence of air <00JA5012>. 

Less extended investigations have been carried out for the stereochemistry of further substitution reactions, which mostly proceed with lower regioselectivities a-carboxylation (inversion) reaction with methyl chloroformate in the a-position (inversion) a-acylation by 2,2-dimethylpropanoyl chloride (inversion)" y-methylation by methyl iodide (anti-S g) and methyl triflate syn-S f° , intramolecular reactions with allyl chlorides (a, inversion or y, awh -S see Section IV.C.3). 

Alkylation of cyclopropanecarboxylic acid esters,6 Deprotonation of methyl silyloxycyclopropanecarboxylates (1), prepared as shown, is possible with LDA in THF at — 78°. The resulting anions react with primary alkyl iodides and benzylic or allylic bromides to give 2 in high yield. These products are cleaved by F to methyl 4-ketocarboxylates 3. 

Catalyst screening experiments resulted in the discovery that copper(salen) complex 33 was a highly effective catalyst for the conversion of alanine derivative 16b into (f )-a-methyl phenylalanine 17 under the conditions shown in Scheme 8.16. The presence of just 1 mol% of catalyst 33 was sufficient to induce the formation of compound 17 with up to 92% ee and in >70% yield [33]. Allyl bromide, 1-chloromethylnaphthalene and ethyl iodide also reacted with substrate 16b to give the corresponding (H)-a-methyl a-amino acids in the presence of 2 mol % of complex 33 [34], Complex 33 also catalyzed the asymmetric mono-alkylation of glycine-derived substrate 34 by benzylic or allylic halides, to give (H)-a-amino acid derivatives 35 with 77-81% ee. and in greater than 90% yield, as shown in Scheme 8.17. 

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