Allyl organometallic compounds reviews

For a review of reactions of allylic organometallic compounds, see Courtois, G. Miginiac, L. J. Organomet. Chem., 1974, 69, 1-44. 

The fairly recent literature has included a review of the preparation and reactions of allyl and butenyl Grignard reagents (5), a review of the reactions of allylic organometallic compounds (II), and a review of organomagnesium rearrangements, in which allylic derivatives were discussed in some detail (29). Since more recent publications do not appear to include new information that would significantly modify earlier conclusions, the previous discussions should suffice. 

Silicon-based Lewis acids have been known for some time, and the related chemistry in catalysis has recently been reviewed [24]. Most examples in the literature are mainly based on achiral species and will be discussed only briefly in this section. In general, a broad variety of reactions can be catalyzed with compounds like MejSiOTf, MejSiNTf or MOjSiClO. One advantage over some metal Lewis acids is that they are compatible with many carbon nucleophiles like silyl enol ethers, allyl organometallic reagents and cuprates. 

In systems where the molecular orbitals have a similar atomic basis, as in the molecules discussed in this review, it is usually found that the sequence of ionization energies and orbital energies is the same although the absolute values do not agree, as for example in Table 1. Should there be a discrepancy in sequence there is said to be a failure of Koopmans theorem , examples of which are common especially for molecules where the atomic bases differ as, for instance, in organometallic compounds like ferrocene and bis-(7i-allyl)nickeP . Further examples can be found in Refs 38-44. 

The intramolecular [4+3] cycloaddition reaction towards seven-membered rings involving furans and allylic cations have been reviewed <01ACR595>. A review on the use of 2-siloxyfurans as butenolide precursors has appeared <01T3221>. Organometallic compounds of furans and their benzoannulated derivatives have also been summarized <01 AHCI>. 

Organometallic Compounds of Palladium and Platinum. The period of this review has been one of rapid advance in the field of oiganopalladiumand organoplatinum structural chemistry. Particular attention has been focused on platinum(0) and platinum(n) complexes of olefins and similar unsaturated molecules for palladium the major emphasis has been on allyl complexes. 

Abstract The purpose of this chapter is to present a survey of the organometallic chemistry and catalysis of rhodium and iridium related to the oxidation of organic substrates that has been developed over the last 5 years, placing special emphasis on reactions or processes involving environmentally friendly oxidants. Iridium-based catalysts appear to be promising candidates for the oxidation of alcohols to aldehydes/ketones as products or as intermediates for heterocyclic compounds or domino reactions. Rhodium complexes seem to be more appropriate for the oxygenation of alkenes. In addition to catalytic allylic and benzylic oxidation of alkenes, recent advances in vinylic oxygenations have been focused on stoichiometric reactions. This review offers an overview of these reactions... 

Allyl complexes have contributed significantly to the development of the organometallic chemistry of nickel and the applications of nickel complexes in organic synthesis, for example, nucleophilic attack on coordinated allyl ligands. In addition, allylnickel complexes have been identified as key intermediates in the oligomerization and cyclization of olefins and dienes. For example, the Ni(0)-catalyzed hydrocyanation of butadiene to adiponitrile, the main component of a major commercial process for the production of nylon, involves Ni (7r-allyl) intermediates. Moreover, the 77-rearrangements of allylnickel species have helped explain the facile isomerization of olefins in the presence of nickel complexes. The Ni-catalyzed homoallylation of carbonyl compounds with 1,3-dienes also involves Ni(7r-allyl) complexes this subject has been reviewed recently. New applications include the cleavage of G-G bonds in the deallylation of malonates, the preparation of cyclopentenones by carbonylative cycloaddi-... 

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