Reactions Of Organometallic Compounds Research Articles

Evidence for single electron transfer in the reactions of organometallic compounds with 2,3,3-trimethyl-2-butyl peroxybenzoate

Utilization of a triptoxy radical probe in the reactions of organometallic compounds with 2,3,3-trimethyl-2-butyl peroxybenzoate indicates that the radical character of the reaction decreases in the order n -BuLi > n -BuMgCl > PhMgBr.

Reactions of organometallic compounds, catalyzed by transition metal complexes. 7. Oxidative demercuration of arylmercury in the presence of complexes of palladium and rhodium

1. The effects of adding halide ion, type of solvent and catalyst on the oxidative demercuration of arylmercury compounds in the presence of palladium and platinum complexes have been studied. 2. In the presence of halide ion, arylmercury compounds Ar2Hg and ArHgX (Ar=p-ClC6H4, Ph, P-MeC6-H4, p-MeOC6H4, p-Me2NC6H4, p-H2NC6H4, 2-thienyl; X=Cl, OAc) undergo oxidative demercuration catalyzed by palladium and rhodium complexes, under very mild conditions (20°C), to give symmetrical diaryls in high yields.

Reactions of organometallic compounds, catalyzed by transition metal complexes. 8. Carbonylation of arylmercury compounds in the presence of palladium and rhodium

1. It has been found that in the presence of iodide ion the carbonylation of arylmereury compounds R2Hg and RHgX (R=p-ClC6H4, Ph, p-MeC6H4, p-MeOC6H4, p-Me2NC6H4, p-H2NC6H4, o-HOC6H4, 2-thienyl; X=Cl, Br, OAc), catalyzed by palladium and rhodium complexes, proceeds under very mild conditions (1 atm CO, 20°C) to give high yields of symmetrical diaryl ketones. 2. The effects of type of solvent and catalyst, and the type and amount of halide ion have been examined, and the optimum conditions for carbonylation have been found.

Reactions of organometallic compounds catalyzed by transition metal complexes. Communication 6. Reactions of organomercury compounds with acid chlorides in the presence of palladium, nickel, and rhodium complexes

1. A study was carried out on the effect of solvent, catalyst, and halide ion additives on the acyldemetallation of organomercury compounds in the presence of palladium, nickel, and rhodium complexes. Optimal conditions were found for carrying out the acyldemercuration both for R2Hg and RHgX, where R=aryl and alkyl groups. 2. Convenient methods were developed for the synthesis of substituted benzophenones, alkylaromatic, unsaturated, and heterocyclic ketones.

Reactions of organometallic compounds catalyzed by complexes of transition metals Communication 5. Organomagnesium, -zinc, -cadmium, and -aluminum compounds in allyldemetallation reactions catalyzed by palladium complexes

1. Reactions of organometallic compounds RM (R=Ph, p-MeC6H4, p-BrC6H4, p-MeOC6H4, p-Me2NC6H4, PhCH2, PhCH=CH, 9-fluorenyl, 2-thienyl, PhC≡C; M=MgBr, ZnCl, CdBr, AlCl2) with CH2=CHCH2X (X = Br, OAc, OPh,+NEt3) catalyzedby Pd(PPh3)4 and (λ3-C3H5PdCl)2 in THF have been studied. The influence has been investigated of the nature of metal M, of the organic radical R, and of the leaving group X on the rate of allyl-demetallation and on the yield of products RCH2CH=CH2 and R2. 2. The reactions of RMgBr (R=Ph, p-MeC6H4, p-BrC6H4, PhCH2, 9-fluorenyl, 2-thienyl) with CH2=CHCH2Br catalyzed by Pd(PPh3)4 proceeded significantly more rapidly and selectively than in the absence of palladium catalyst which made it possible to obtain the corresponding products of allyldemetallation under mild conditions and in high yield. 3. The main possibility of allyldemetallation of Reformatsky reagents has been shown for the first time in the example of the reaction of BrZnCH2CO2Et with CH2=CHCH2Br catalyzed by (λ3-C3H5PdCl)2 and leading to the preparation of CH2=CHCH2CO2Et. The reaction is a convenient method for introducing the allyl group into theα-position of esters.

けい素陰イオンおよび関連種の化学 最近の進歩

Syntheses and reactions of organometallic compounds having Si-Mtl bond as well as “metal free” silyl anion species are reviewed in the order of the periodic classification of metal elements. With these reagents, silyl groups are successfully introduced into organic substrates by (1) substitution of halogen of alkyl, allyl, aryl, vinyl, and acyl halides, (2) addition to ketone and aldehyde carbonyls, and (3) addition to alkynes, allenes, and conjugated dienes. These reactions are useful for synthesis of versatile organosilicon compounds.

Reactive organometallic compounds from metallocenes

Abstract

Paramagnetic products formed in the reactions of organometallic compounds. XII ESR study of oxido anion substituted diaryl ketyl radicals

AbstractIn the reactions of alkyl‐substituted‐benzenecarboxylic and ‐2‐hydroxybenzenecarboxylic acids (ArCOOH) with alkyl‐substituted phenyl Grignard reagents (RMgX) in the presence of nickel, ketyl radicals ArCO−R are formed. The para substituents (H, Me, Et, Isopr and t‐Bu) of R increase the non‐equivalence of its ortho protons (a change of a2H = 0.43 mT, a6H = 0.422 mT to 0.435 mT, 0.395mT respectively, on substituting t‐butyl for H at position 4). The oxido anion group originating from 2‐hydroxybenzenecarboxylic acid has a strong push effect and nearly doubles the unpaired spin density on the phenyl ring R.

特徴的な電解反応の有機合成への応用

This review is organized under the following headings with 440 references.1. Generation and reactions of reactive intermediates.1.1. Carbon species. 1.2. Nitrogen species. 1.3. Oxygen species. 1.4. Others.2. Reactions of organic hetero atoms.2.1. Nitrogen. 2.2. Sulfur. 2.3. Phosphorus and others.3. Formation and reactions of organometallic compounds.3.1. Formation of metallic compounds employing electrodes as a metal source.3.2. Conversion of metallic compounds to other metallic compounds. 3.3. Formation of nonmetallic compounds from metallic compounds.4. Bimolecular reactions.4.1. Dimerization. 4.2. Cyclization. 4.3. Ring expansion and contraction.5. Stereochemistry.5.1. Stereoselective and stereospecific reactions. 5.2. Asymmetric reactions and asymmetric syntheses.6. New type reactions.

有機合成に用いられる金属化合物の合成と性質 Ｚｒ Ａｐｐｌｉｃａｔｉｏｎ ｏｆ ｏｒｇａｎｏｚｉｒｃｏｎｉｕｍ ｃｏｍｐｌｅｘｅｓ ｉｎ ｏｒｇａｎｉｃ ｓｙｎｔｈｅｓｉｓ （有機合成における有機ジルコニウム錯体の応用）

Hydrozirconation using chlorobis (η-cyclopentadienyl) hydridozirconium (IV) is a useful procedure for functionalizing alkenes, alkynes, and 1, 3-dienes via organozirconium (IV) intermediates. These intermediates react with a variety of electrophilic reagents to give organic products in high yield. Via transmetalation the zirconium intermediates also serve as precursors of reactive organometallic compounds of metallic elements whose chemistry is well established with regard to C-C bond formation processes. Some typical experimental procedures are described.

Reactions of organometallic compounds and groups with sterically hindered o-quinones

1. We have suggested a scheme for the one-electron oxidation of group II OMC by substituted o-quinones. 2. The influence of the nature of the radicals R attached to mercury on the hyperfine coupling constantaHg is related to the changes in the geometric configuration of the unit caused by changes in the bulk of the substituent R.

On the mechanisms of substitution reactions of organometallic compounds of nontransition metals

Abstract

Mo-theoretical characterization of organic reaction mechanisms VII. (2 + 2) Reactions of organometallic compounds

The concept of the triplet instability for the conventional Hartree—Fock molecular orbitals has been applied to thermal (2 + 2) reactions of organo- metallic compounds. It is found that the olefin insertions into metal—hydro- gen bonds (metal = Al, B, and Ti) proceed without radical character, while the reaction of the Ni analog must bear some biradical character. These reactions follow mechanisms distinct from those for familiar symmetry- forbidden (2 + 2) reactions. The difference in mechanism is ascribable to the advantageous participation of a vacant p orbital (for Al and B) or d symmetry orbitals (for Ti and Ni) in reactions. The catalytic cleavage of ethylene oxide and the addition of a Grignard reagent to nitrile also fall under the category of symmetry-forbidden nonradical processes. The hydrogenation of binuclear aluminum hydride, however, should possess a significant biradical character.

Etude comparative du comportement d'organometalliques allyliques et d'organolithiens satures vis a vis de carbures: RCH≡CHC≡CR′ et RC≡CC≡CR′ (R [dbnd] alcoyle, R′ [dbnd] H, alcoyle

Summary Reactive organometallic compounds such as allyl-zinc, -magnesium and -lithium and saturated lithium compounds are shown to readily undergo addition reactions with conjugated enynes and conjugated diynes: RCH CHC≡CH and RC≡CC≡CH; this reaction is regioselective and leads to conjugated dienes, conjugated enynes or allenes. The reactivity is reduced with conjugated enynes: RCH CHC≡CR′, but organo-magnesium and -lithium compounds lead to allenes. The reaction does not take place with conjugated diynes: RC≡CC≡CR′, under normal conditions.

Etude du comportement d'organometalliques (M = Zn, Mg, Li) vis a vis d'enynes conjuges : I. Cas des carbures: HCCC(R)C(R)(R); influence de la structure sur la reactivite et la regioselectivite

Reactive organometallic compounds such as allyl-zinc, -magnesium, -lithium and saturated lithium compounds are shown to readily undergo addition reactions with conjugated enynes: HCCC(R)C(R)(R), but the reactivity is reduced when the steric hindrance around the double bond is increased. With each organometallic compound used, this reaction is regioselective: 3,4 addition with organozinc compounds, 1,2 addition with organolithium compounds (allyl, butyl) and both 1,2 and 1,4 addition with organomagnesium compounds.

Etude du comportement d'organometalliques (M = Zn, Mg, Li) vis a vis d'enynes conjugues : II. Cas des enynes fonctionnels: HCCC(R)C(R′)(CH 2) nR″; Influence de la structure sur la reactivite et la regioselectivite

Reactive organometallic compounds such as allyl-zinc, -magnesium,-lithium and saturated lithium compounds are shown to readily undergo addition reactions with functionally conjugated enynes: HCCC(R)C(R′)(CH 2) n R″ (R″ = OH, OC 4H 9, NHC 2H 5N(C 2H 5) 2), but the reactivity is reduced when the steric hindrance around the double bond is increased. With each organometallic compound used, this reaction is regioselective: 3,4 addition with organozinc compounds, 1,2 addition with organolithium compounds (allyl-, butyl-) and both 1,2 and 1,4 addition with organomagnesium compounds.

ChemInform Abstract: SOLVENT EFFECTS ON THE REACTIVITIES OF ORGANOMETALLIC COMPOUNDS

Chemischer InformationsdienstVolume 7, Issue 24 Organoelement Compounds ChemInform Abstract: SOLVENT EFFECTS ON THE REACTIVITIES OF ORGANOMETALLIC COMPOUNDS V. GUTMANN, V. GUTMANNSearch for more papers by this author V. GUTMANN, V. GUTMANNSearch for more papers by this author First published: June 15, 1976 https://doi.org/10.1002/chin.197624304Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume7, Issue24June 15, 1976 RelatedInformation

Solvent effects on the reactivities of organometallic compounds

Solvent effects on the reactivities of organometallic compounds

Evidence for intermediate formation of homolytic particles in reaction of organometallic compounds with 2,2,6,6-tetramethyl-1-oxopiperidinium salts

Evidence for intermediate formation of homolytic particles in reaction of organometallic compounds with 2,2,6,6-tetramethyl-1-oxopiperidinium salts

Mechanism of reactions of organometallic compounds with organic halides

It was shown that the basic rules of the reactions of organometallic compounds with organic halides, in particular, the formation of free radicals in these reactions, can be explained within the framework of the theory of molecular Orbitals and their interactions.