Addition transformations naming

The capability of L-proline - as a simple amino acid from the chiral pool - to act like an enzyme has been shown by List, Lemer und Barbas III [4] for one of the most important organic asymmetric transformations, namely the catalytic aldol reaction [5]. In addition, all the above-mentioned requirements have been fulfilled. In the described experiments the conversion of acetone with an aldehyde resulted in the formation of the desired aldol products in satisfying to very good yields and with enantioselectivities of up to 96% ee (Scheme 1) [4], It is noteworthy that, in a similar manner to enzymatic conversions with aldolases of type I or II, a direct asymmetric aldol reaction was achieved when using L-proline as a catalyst. Accordingly the use of enol derivatives of the ketone component is not necessary, that is, ketones (acting as donors) can be used directly without previous modification [6]. So far, most of the asymmetric catalytic aldol reactions with synthetic catalysts require the utilization of enol derivatives [5]. The first direct catalytic asymmetric aldol reaction in the presence of a chiral heterobimetallic catalyst has recently been reported by the Shibasaki group [7]. 

A thoughtful reader would have noticed that, while plenty of methods are available for the reductive transformation of functionalized moieties into the parent saturated fragments, we have not referred to the reverse synthetic transformations, namely oxidative transformations of the C-H bond in hydrocarbons. This is not a fortuitous omission. The point is that the introduction of functional substituents in an alkane fragment (in a real sequence, not in the course of retrosynthetic analysis) is a problem of formidable complexity. The nature of the difficulty is not the lack of appropriate reactions - they do exist, like the classical homolytic processes, chlorination, nitration, or oxidation. However, as is typical for organic molecules, there are many C-H bonds capable of participating in these reactions in an indiscriminate fashion and the result is a problem of selective functionalization at a chosen site of the saturated hydrocarbon. At the same time, it is comparatively easy to introduce, selectively, an additional functionality at the saturated center, provided some function is already present in the molecule. Examples of this type of non-isohypsic (oxidative) transformation are given by the allylic oxidation of alkenes by Se02 into respective a,/3-unsaturated aldehydes, or a-bromination of ketones or carboxylic acids, as well as allylic bromination of alkenes with NBS (Scheme 2.64). 

Studies on thebiomimetic synthesis of quinone antibiotics [191] led Krohn to yet another type of enantioselective transformation, namely microbial conversion of an achiral substrate into enantiomericaUy pure anthracych-nones. An adroit synthesis of the microbial transformation substrate, 4-deoxyaklanonic acid (202) [192] (Scheme 38), started from homophthahc ester 196 [193] with addition of diUthiated tert-butyl acetoacetate (197) and subsequent cychzation to isocoumarine 198 [194]. Reaction of 198 with the dilithium salt 199 gave anthrone 200 [195[. Aeration of 200 in the pres-... 

In 2013 Cozzi et al. prepared the 2-(diethylferrocenyl) pyrrolidine (S)-36 starting from ferrocenyl ethyl ketone (Scheme 11.37) and proved its effectiveness in different organocatalytic transformations, namely the Michael addition of aliphatic aldehydes to aromatic nitroalkenes (Scheme 11.38A) and the SNl-asymmetric a-allgflation of carhonyl compounds (Scheme 11.38B). ... 

Regarding the third vector, during the last few years there has been significant progress in the synthetic methods that lead to formation of self-organized macromolecular structures, based on the concept of end-groups attractive/repulsive interactions or formation of block copolymers, namely HyperMacs and HyperBlocks. " Control of chain ends also offers means for efficient control of the surface properties, e.g., addition of < 0.5% of multi-functional fluoroalkyl additives transforms PS surface tension to that of PTFE. ... 

A domino Diels-Alder reaction (the term was chosen from the well-known game) is a one-pot process involving two or more Diels-Alder reactions carried out under the same reaction conditions without adding additional reagents or catalyst such that the second, third, etc., cycloaddition is the consequence of the functionality generated in the previous reaction. A historical example is illustrated in Equation 1.28 [60]. This type of transformation is sometimes named tandem or cascade, but these terms seem less appropriate for describing a time-resolved transformation. 

When a general group (such as halo) is used, its priority is that of the lowest member of its group (see footnote 913). Thus the general name for this transformation is halo-alkylsulfonyl-addition because halo has the same priority as fluoro, its lowest member. 

The lUPAC names for organic transformations, first introduced in the Third Edition, is included. Since then the rules have been broadened to cover additional cases hence more such names are given in this edition. Furthermore, lUPAC has now published a new system for designating reaction mechanisms (see p. 384), and some of the simpler designations are included. 

The user is able to customize the transform setup resource file to include as many custom scripts or unit transforms as desired for a particular application. In addition, the user can improvise operations on the fly. If the analyst decides to try plotting the data as a function of a reciprocal log, he takes the log and then reciprocal of the x-axis. If he decides to make this a regular option, he can enter it in the transform setup list under any name desired. Next time the transform option is called he will be able to select that operation by choosing it from the list under the name saved under. 

This chapter will also deal with compounds containing two or three phosphinous amide units, which, for simpUcity, will be named here as bis(amino-phosphanes) or tris(aminophosphanes) but not with phosphinous amides containing other additional organophosphorus functionaUties as, for instance, the so-called aminophosphine phosphinites (AMMP), which have been the subject of increasing attention in the Uterature dealing with catalytic asymmetric transformations and have been treated in other reviews [2,3]. 

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