Barbier review

For a review of catalyst poisoning by sulfur, see Barbier Lamy-Pitara Marecot Boitiaux Cosyns Verna Adv. 

For a review of diiodosamarium chemistry (including Barbier Reactions) see ... 

Sulfur is generally considered to be a poison of hydrogenation reactions. However, in commercial hydrogenation and dehydrogenation reactions, sulfur is also used as a modifier, and in some cases as activator of catalytic hydrogenation reactions. Barbier and co-authors review the Role of Sulfur in Catalytic Hydrogenation Reactions. ... 

An indium-mediated ring-expansion reaction of a cyclic thioether derivative 31 in aqueous medium leads to the eight-membered cyclic thioether derivative 32, which isomerizes to the more stable conjugated product 33 in 62% yield (referred to 31) (Scheme 10) <1999SL735>. For a review of such Barbier-Grignard type reactions in water see <1996T5643>. 

The use of ultrasonic techniques in virtually every field of chemistry has expanded greatly in recent years. Sonochemical methods have probably been most successful for heterogeneous reactions in general and, in particular, for organometallic synthesis. Ultrasonic synthesis allows the use of safer solvents that need not be anhydrous, cheaper chloride starting materials and, frequently, lower reaction temperatures. An excellent review-on the use of sonochemistry in organic and organometallic chemistry is that of Einhorn and co-workers [141]. A second Einhorn publication on the ultrasonically assisted Barbier reaction is also very informative [142],... 

The Barbier reaction with other metals can occupy an entire volume on its own and, hence, will not be reviewed in this work. The interested reader should refer to the references cited at the beginning of this text and those noted in the following for additional information. 

In the last 10 years, the Barbier reaction method has been utilized more with other metals than with magnesium. The number of papers published on the lithium-Barbier reaction is three to four times that of magnesium [149-157]. Reactions can be carried out at lower temperatures than possible with Mg-Barbier reactions and yields are often very high with fewer by-products. Other metals of note are samarium, in the form of its diiodide [158-165], and zine [166-169], the metal of choice for the pre-Barbier one-step reaction, and the classic Reformatsky reaction. In situ reactions have been reported for A1 [170], Ce [171], Cd [172,173], Ga [174], Hg [175], In [176], Mn [177], Pb [178-180], Sb [181-183], Sn [184,185], and Ti [186]. An excellent paper by Li reviews the Barbier reactions of many metals in aqueous media [187]. 

In addition to its role as a reactant for CO removal by water-gas shift, steam can contribute to the removal of hydrocarbons via steam reforming. Steam reforming is indeed an industrial process, which is used for the production of hydrogen or syngas (Duprez 1992). Steam effects in three-way catalysis have been reviewed by Barbier and Duprez 1994, accordingly we will focus only on some relevant aspects related to the role of Ce02. 

The application of indium- and tin-mediated Barbier-Grignard reactions in aqueous solution to the chain extension of unprotected sugars has been reviewed. Some C-5 variants of iV-acetylneuraminic acid have been prepared by the indium-mediated addition of ethyl oc-(bromomethyl)acrylate to variously N-substituted mannosamines," and similar chemistry using (bromomethyl)vinyl phosphonate has led to the phosphonate analogue 12. The reaction of O-protected aldono-1,4- and -1,5-lactones with (2-bromomethyl)-acrylate or -acrylonitrile or 2-bromobutyrolactone mediated by samarium diodide led to chain-extended ulosonic acid derivatives." ... 

Early review D. A. Shirley, Org. React. 8,28-58 (1954). Preparation of Grignard reagents Y. H. Lai, Synthesis 1981, 585-604. Mechanistic study K. Maruyama, T. Katagiri, J. Phys. Org. Chem. 2, 205 (1989). Review of stereoselective addition of carbonyl compounds D. M. Huryn, Comp. Org. Syn. 1, 49-75 (1991). General review G. S. Silverman, P. E. Rakita in Kirk-Othmer Encyclopedia of Chemical Technology ot 12 (Wiley-Interscience, New York, 4th ed., 1994) pp 768-786. Cf. Barbier(-tvpe) Reaction. 

Benezra C, Stampf J-L, Barbier P, Ducombs G (1985) Enantio-specificity in allergic contact dermatitis. A review and new results in Frullania-sensitive patients. Contact Dermatitis 13 110-114... 

The formation of an organometallic reagent in the presence of an electrophilic partner is a synthetic process of historical value, illustrated by the Barbier and Reformatsky reactions. In their first versions, these processes consisted of additions to carbonyl compounds. They have now been extended to a wide variety of substrates and were reviewed in a recent book.250... 

Unknown Reaction. It is of historical and scientific interest to consider the reasons why the Barbier reaction has only recently drawn the significant attention of synthetic organic chemists. The first review article of the field was published in 1977 [44], more than three quarters of a century after the reaction was first discovered. 

Chapter 2 of this monograph will present as complete a review as necessary of the application of the Barbier reaction procedures as published till 1990 and where possible till 1991. 

The investigations in which other halides were used as well as the studies of the mechanistic aspects of the Barbier reaction will be reviewed elsewhere in this monograph (pp. 60-68 and Sect. 4.4). 

Even fluorobenzene forms the corresponding Grignard compound at a temperature of — 20 °C. Although in the review article, no mention is made of Barbier reactions carried out with Mg/Gr, it was mentioned (from unpublished work) that... 

Sonication, The introduction of sonication (for a recent review on sonication see [31]) in Li-Barbier chemistry [32] has enhanced the synthetic importance of this procedure ... 

My earliest activities in this field include a modest and first-ever review article (in cooperation with Dr. F. A. Hartog who at that time (1977) did his doctoral research on the Barbier reaction). References to this review article, as mentioned in the Science Citation Index till recently are a good indication for a continued interest in this simple synthetic procedure. 

A good number of reviews, perspectives, highlights, focus, and account of research were published in the period under review. The topics covered included nitfation of aromatic compounds, oxidation processes, Pd catalysis, oxidative coupling, asymmetric transfer hydrogenation, Sm-Barbier reaction, use of hypervalent I2, and Bayer-Villiger reaction. 

A Lewis acid push-pull mechanism proposed for the magnesium bromide promoted Barbier-type intramolecular cyclization of Grignard reagents derived from halo-substituted acetals, ketals, and orthoesters as depicted in (Scheme 9). Stereoselective addition of chiral a-aminoorganometallics to aldehydes has been reviewed. Chiral 1,4-dihydropyridines have been synthesized with good regio- and... 

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