Synthesis applications with 7-complexes

In recent years the applicability of the Schmidt reaction for the synthesis of more complex molecules—especially the variant employing alkyl azides—has been further investigated. Cycloketones bearing an azidoalkyl side-chain at the a-carbon center have been shown to undergo, upon treatment with trifluoroacetic... 

A direct application of the ring-opening reaction of an epoxide by a metal enolate amide for the synthesis of a complex molecule can be found in the synthesis of the trisubstituted cyclopentane core of brefeldin A (Scheme 8.35) [68a]. For this purpose, treatment of epoxy amide 137 with excess KH in THF gave a smooth cyclization to amide 138, which was subsequently converted into the natural product. No base/solvent combination that would effect cyclization of the corresponding aldehyde or ester could be found. 

The synthesis of these complexes can easily be accomplished by substitution of one or both PCy3 groups of 3 by NHC ligands. The X-ray structure of 6 shows significantly different bond lengths the Schrock double bond to the CHPh group is 1.821(3) A, while the NHC bond to the l,3-diisopropylimidazolin-2-ylidene is 2.107(3) A. Complexes with imidazolidin-2-ylidenes were also synthesized and screened in an extensive study by Fiirstner [153], who found that the performance of those catalysts depends strongly on the application and that... 

Enzymatic polymerizations have been established as a promising and versatile technique in the synthetic toolbox of polymer chemists. The applicability of this technique for homo- and copolymerizations has been known for some time. With the increasing number of reports on the synthesis of more complex structures like block copolymers, graft copolymers, chiral (co)polymers, and chiral crosslinked nanoparticles, its potential further increases. Although not a controlled polymerization technique itself, clever reaction design and integration with other polymerization techniques like controlled radical polymerization allows the procurement of well-defined polymer structures. Specific unique attributes of the enzyme can be applied... 

Pt(S2CNMe(Hex))2] and [Pd(S2CNMe(Hex))2] have been synthesized and used as precursors to grow the first TOPO-capped PtS and PdS nanoparticles and thin films of PtS and PdS by the metallo-organic chemical vapor deposition (MOCVD) method [204]. Platinum and palladium chalcogenides find applications in catalysis [205-210] and materials science [211,212]. The synthesis of thiocarbamato complexes of platinum and palladium from reaction of an aqueous solution of ammonium dithiocarbamate with the platinum or palladium salt has been reported by Nakamoto et al. [213]. However... 

Anthranilic acid (2-aminobenzoic acid) is an N—O bidentate which commonly forms 2 1 complexes with a variety of bivalent metal ions. d Avignon and Brown16 provided details of some of the structures and applications of these chelates. The synthesis of ternary complexes of 2-aminobenzoic acid and l-nitroso-2-naphthol with a variety of transition metal ions has been reported.17 An X-ray structure shows an unusual N monodentate coordination mode to rhodium for the ligand.18... 

Conjugate addition of organocuprates has seen many applications in complex synthesis. For example, in the preparation of an opiate alkaloid it was necessary to introduce a methyl group at a late stage of the synthesis.110 The transformation of (47) to (48) was successfully carried out with Me2CuLi in a stereoselective manner (equation 51). 

As has been mentioned above, the special interest in these derivatives is connected with their application in the synthesis of the complex oxide materials (see Chapter 10 for details). The heterometallic alkoxides have been discussed in a number of reviews, the most complete of those (at different moments in time) being the corresponding chapter in the book by Bradley et al. [223] and articles of Mehrotra [1138] and also of Caulton and Hubert-Pfalz-graf [306],... 

This chapter discusses the application of MINLP methods in the synthesis of reactor networks with complex reactions and in the synthesis of reactor-separator-recycle systems. 

---