Initial Reports

To date, more than twenty X-ray crystal structures of ODCase have been reported, all by the groups of Ealick, Pai, Larsen, and Short and Wolfenden (see Table 1) [14-21]. The first six of these were reviewed previously by Houk, Lee, and coworkers [22] and Begley, Appleby, and Ealick [23]. As noted by these reviewers, the active-site structure of ODCase is extremely similar in all of the reported structures, boasting an Asp-Lys-Asp-Lys tetrad in the vicinity of the 6-position of the pyrimidine 

Date Ligand bound Mutation(s) Organism Resolution (A) Group 

Although no structures of ODCase complexed with its natural substrate (OMP) were available at the time of these reports, several structures complexed to related compounds were described. These compounds (Chart 1) were UMP (the ultimate product of decarboxylation), BMP (a transition 

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The mechanism of initiation in cationic polymerization using Friedel-Crafts acids appeared to be clarified by the discovery that most Friedel-Crafts acids, particularly haUdes of boron, titanium, and tin, require an additional cation source to initiate polymerization. Evidence has been accumulating, however, that in many systems Friedel-Crafts acids alone are able to initiate cationic polymerization. The polymerization of isobutylene for instance can be initiated, reportedly even in the absence of an added initiator, by AlBr or AlCl (19), TiCl ( )- Three fundamentally different... 

Standard Mosquito Repellents. Since its initial report as a promising repellent in 1954, DEET has been considered the best all-around repellent having generally acceptable characteristics, despite a continuing search for a superior chemical. Improvements include many commercial products with added cosmetic agents that use slow release technology, such as the U.S. Armed Services slow release 35% DEET formulation (16). There were 35 EPA-registered repellent products in 1994 that contained only DEET under different trade names (2). DEET is present in 192 of the 212 products mentioned previously (2). 

Titanium Dichloride. Titanium dichloride [10049-06-6] is a black crystalline soHd (mp > 1035 at 10°C, bp > 1500 at 40°C, density 31(40) kg/m ). Initial reports that the titanium atoms occupy alternate layers of octahedral interstices between hexagonaHy close-packed chlorines (analogous to titanium disulfide) have been disputed (120). TiCl2 reacts vigorously with water to form a solution of titanium trichloride andUberate hydrogen. The dichloride is difficult to obtain pure because it slowly disproportionates. 

Carbon nanotube research was greatly stimulated by the initial report of observation of carbon tubules of nanometer dimensions[l] and the subsequent report on the observation of conditions for the synthesis of large quantities of nanotubes[2,3]. Since these early reports, much work has been done, and the results show basically that carbon nanotubes behave like rolled-up cylinders of graphene sheets of bonded carbon atoms, except that the tubule diameters in some cases are small enough to exhibit the effects of one-dimensional (ID) periodicity. In this article, we review simple aspects of the symmetry of carbon nanotubules (both monolayer and multilayer) and comment on the significance of symmetry for the unique properties predicted for carbon nanotubes because of their ID periodicity. 

It should also be noted that the Final Report is not the initial report but the report containing the supplements that indicate all actions to be satisfactorily completed. 

Addition of hydrogen sulfide results in formation of monomeric gem dithiols or trimeric thioketals (511,512). The initially reported thione formation (513-515), analogous to hydration of morpholinocyclohexene... 

In the initial report by Corey and Chaykovsky, dimethylsulfonium methylide (2) reacted smoothly with benzalaniline to provide an entry to 1,2-diphenylaziridine 67. Franzen and Driesen reported the same reaction with 81% yield for 67. In another example, benzylidene-phenylamine reacted with 2 to produce l-(p-methoxyphenyl)-2-phenylaziridine in 71% yield. The same reaction was also carried out using phase-transfer catalysis conditions.Thus aziridine 68 could be generated consistently in good yield (80-94%). Recently, more complex sulfur ylides have been employed to make more functionalized aziridines, as depicted by the reaction between A -sulfonylimine 69 with diphenylsulfonium 3-(trimethylsilyl)propargylide (70) to afford aziridine 71, along with desilylated aziridine 72. ... 

The base-catalysed isomerisation of thiazoles to imidazoles initially reported by Cook et al " has been further investigated more recently. One notable example reports the reaction of 2-amino-2-cyanoacetamide 37 with benzylisothiocyanate to give 5-... 

Subsequent to Hantzsch s communication for the construction of pyridine derivatives, a number of other groups have reported their efforts towards the synthesis of the pyridine heterocyclic framework. Initially, the protocol was modified by Beyer and later by Knoevenagel to allow preparation of unsymmetrical 1,4-dihydropyridines by condensation of an alkylidene or arylidene P-dicarbonyl compound with a P-amino-a,P-unsaturated carbonyl compound. Following these initial reports, additional modifications were communicated and since these other methods fall under the condensation approach, they will be presented as variations, although each of them has attained the status of named reaction . 

Condensation of Af-aryliminochlorides with malonic ester followed by thermal cyclization, as initially reported by Just, was found to be a general method for the preparation of 2, 3, 4-substituted quinolines. Various substituents on the aryl ring of the iminochloride proved uneventful, even though the conditions required to generate the iminochloride utilized PCI5. 

Since Evans s initial report, several chiral Lewis acids with copper as the central metal have been reported. Davies et al. and Ghosh et al. independently developed a bis(oxazoline) ligand prepared from aminoindanol, and applied the copper complex of this ligand to the asymmetric Diels-Alder reaction. Davies varied the link between the two oxazolines and found that cyclopropyl is the best connector (see catalyst 26), giving the cycloadduct of acryloyloxazolidinone and cyclopentadiene in high optical purity (98.4% ee) [35] (Scheme 1.45). Ghosh et al., on the other hand, obtained the same cycloadduct in 99% ee by the use of unsubstituted ligand (see catalyst 27) [36] (Scheme 1.46, Table 1.19). 

This review outlines developments in zinc-mediated cyclopropanation from the initial reports in the 1950s through to the current state of the art methods. The presentation will rely heavily on how the evolution of mechanistic understanding aided in the rationalization and optimization of each new advance in the asymmetric process. 

These initial reports demonstrated that a catalytic asymmetric variant of the Simmons-Smith reaction could be developed. Although good yields and selectivities were obtained, the lack of a clear understanding of the origin of activation, the limited structural information on the active species and the absence of a stereochemical model made rational improvements difficult at best. The next... 

Since it is often difficult to visualise the extent of attack in terms of depth from such mass-loss units as mdd, it is common practice to convert these mdd figures into others to indicate depth of penetration, i.e. inches per year (ipy), mils or mm y" . Such calculations suffer from the same defects as the mdd figures in that they take into account neither changes in corrosion rates with time nor non-uniform distribution of corrosion. However, since such conversions are often made it is desirable for the initial reporter of the test results to make the calculations accurately and to report corrosion rates in both mdd and mm y or similar units. 

Asymmetric epoxidations of alkenes have been intensively studied since Sharpless initial report on asymmetric epoxidation of allylic alcohols in 1980. This reaction, discussed in Section 9.1.3, has become one of the most widely employed reactions in asymmetric synthesis, due to its reliability and high enantioselectivity [2],... 

Transition metal catalysts arc characterized by their redox ehemistry (catalysts can be considered as one electron oxidants/reductants). They may also be categorized by their halogen affinity. While in the initial reports on ATRP (and in most subsequent work) copper266,267 or ruthenium complexes267 were used, a wide range of transition metal complexes have been used as catalysts in ATRP. 

Subsequent to the initial report by Badley et al. two communications appeared, which reported structural investigations on several products obtained from PtCl4 , methyl isocyanide, and hydrazine 33, 117) these compounds had previously been identified (incorrectly) as six-coordinate platinum(II) species 90). In addition, synthesis work in this area was extended somewhat further by these groups. The details of this work presented in these communications and in later full papers 34, 117) are summarized hy Eqs. (17). 

Since the initial report on the addition reactions of palladium(II) and platinum(II) isocyanide complexes by Badley et al. (S), a rather substantial number of further examples have been reported. These are summarized in Table II. 

Although the initially reported tissue compatibility tests for subcutaneous implants of poly(BPA-iminocarbonate) were encouraging (41,42), it is doubtful whether this polymer will pass more stringent biocompatibility tests. In correspondence with the properties of most synthetic phenols, BPA is a known irritant and most recent results indicate that BPA is cytotoxic toward chick embryo fibroblasts in vitro (43). Thus, initial results indicate that poly(BPA-iminocarbonate) is a polymer with highly promising material properties, whose ultimate applicability as a biomaterial is questionable due to the possible toxicity of its monomeric building blocks. 

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