Organometallic reagents synthetic utility

Some structural aspects of the organometallic compounds of the alkali metals have already been briefly mentioned in Section 4.3.6. The diagonal relation of Li with Mg (p. 76), coupled with the known synthetic utility of Grignard reagents (pp. 132-5), suggests that Li, and perhaps the other alkali metals, might afford synthetically... 

Intramolecular [3-1-2] cycloadditions, i.e., having the TMM moiety and the acceptor linked by a tether, have great synthetic utility in polycarbocycle construction. The construction of 5.5, 6.5, and 7.5 ring systems has been demonstrated with this methodology [21-25]. A number of efficient routes to acyclic precursors were developed (Scheme 2.11). The organometallic reagent (31), generated from 2-bro-mo-3-(trimethylsilyl)propene (32) [26], is a key component in the construction of... 

Carbon-carbon bond formation is the most important reaction in synthetic organic chemistry. Various carbon sources can be utilized for the construction of carbon skeletons. Carbon dioxide (C02) is a nontoxic, cheap, and attractive Ci-source.1,la ld The incorporation of C02 into organic compounds can be achieved by use of various organometallic reagents or catalysts, especially those of transition metals.2 2a 2d This chapter focuses on the carbon-carbon bond formation reactions between C02 and acetylenes and dienes, and covers literature from 1993 to 2004. Subsections are categorized according to metals. 

J. Ji, S. Narayan-Sarathy, R.H. Neilson, J.D. Oxley, D.A. Babb, N.G. Rondon, and W.S. Jr. Smith, [p-( (Trifluorovinyl)oxy)phenyl]lithium formation, synthetic utility, and theoretical support for a versatile new reagent in fluoropolymer chemistry, Organometallics, 17 783-785 (1998). 

The preparation of organolithiums by reaction (a) is of limited synthetic utility because the organomercurlals are prepared from other organometallic reagents, most often organomagnesium halides or organolithiums. In addition, reaction (a) is slow, although ultrasonic irradiation increases the rate. 

In this chapter, the substitution reactions of organometallic reagents with organic halides and related electrophiles are reviewed. - The major portion of the chapter is devoted to a discussion of organocopper compounds, which first transformed the alkylation of nonstabilized carbanions into a reaction of general synthetic utility. More recently, transition metals other than copper have also found widespread application in such coupling reactions, and developments in this area are outlined in Section 1.5.3. 

The present reaction offers a high synthetic utility since functional groups on the aromatic ring, sensitive to organometallic reagents, are compatible moreover, it... 

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