Schmidt reaction tables

In Table 1 the data are summarized from a number of Schmidt reactions carried out with unsymmetricul ketones. 

Table 2 presents some examples of liquid-phase Claisen-Schmidt reactions. 

Table of Compounds Pbbpabed by the Schmidt Reaction—Continued... 

Table op Compounds Pbepabbd bt the Schmidt Reaction—Coniimted... 

The first synthetically useful Schmidt reactions of alkyl azides with ketones were intramolecular. Thus, it was shown that azido-tethered ketones, when treated with Brpnsted or Lewis adds in CH2CI2 at room temperature, were converted to lactams in good to excellent yields (Table 7.1). Mono- and bicyclic ketones are attractive substrates for the preparation of fused bi- and tricyclic lactams and the range of ring sizes accommodated... 

Table 7.1 Intramolecular Schmidt reactions of cyclic azidoketones "... 

Table 7.2 Intramolecular Schmidt reactions of acyclic ketones and aldehydes...

Table 7.5 Hg(OTf)2-promoted Schmidt reactions with NaBH4 workup...

Toste and coworkers have shown that intramolecular Schmidt reactions of acetylenic azides were possible through Au(I) catalysis. Thus, treatment of a series of acetylenic azides with (dppm)Au2Cl2 provides pyrroles in good yields (Table 7.6). These reactions were tolerant of varying substitution and chemoselective when a 1,5-enyne was present, the desired cyclization still proceeded, albeit with reduced efficiency (entry 5). 

Table 6.6 lists some reactions of the electron in water, ammonia, and alcohols. These are not exhaustive, but have been chosen for the sake of analyzing reaction mechanisms. Only three alcohols—methanol, ethanol, and 2-propanol—are included where intercomparison can be effected. On the theoretical side, Marcus (1965a, b) applied his electron transfer concept (Marcus, 1964) to reactions of es. The Russian school simultaneously pursued the topic vigorously (Levich, 1966 Dogonadze et al, 1969 Dogonadze, 1971 Vorotyntsev et al, 1970 see also Schmidt, 1973). Kestner and Logan (1972) pointed out the similarity between the Marcus theory and the theories of the Russian school. The experimental features of eh reactions have been detailed by Hart and Anbar (1970), and a review of various es reactions has been presented by Matheson (1975). Bolton and Freeman (1976) have discussed solvent effects on es reaction rates in water and in alcohols. 

Movassaghi and Schmidt reported that amidation of unactivated esters also occurs in the presence of carbene 3 when 1,2-amino alcohols are nsed [138], A representative sample of the range of esters 277 and amino alcohols 278 is shown in Table 24. A few snbstrates proved problematic under standard reaction conditions. 

Hydroxy activation of 29a using the Mitsunobu reaction gave the corresponding /3-ester derivatives 139. The Schmidt procedure was also superior (Table 9) <2002EJ0113>. 

The reaction of alcohols with diarylcarbodiimides [16, 35, 36] is catalyzed by sodium alkoxides but not by triethylamine. Recently Schmidt and Moos-miiller [37, 38] found that cuprous chloride (0.075 mole/100 mmole dialkyl-carbodiimide) catalyzes the reaction of primary, secondary, and tertiary alcohols with aliphatic carbodiimides to give O Af -trialkylpseudoureas. Several examples of the use of these methods are described in Tables I and II. 

Heterogeneous reaction mechanisms range from the very simple to the complex. Many features of the formalism presented in this chapter are illustrated by the catalytic combustion reaction mechanism given in Table 11.1. The surface-reaction mechanism is due to Sidwell et al. [361], which in turn had its origins with the work of Schmidt [173,174] and Deutschmann [96,97,101],... 

By a parametric study we mean a presentation of the way in which the performance of the system depends on the choice of a parameter. If we want to make a parametric study of the effect of variations of, say, temperature, which affects k but nothing else, this form is ideal, because k is present in Da but in no other parameter. We perform a quick computation of the conversion (%) and time to reach 99% of steady state (min), for U = 0, 0 = 12 s, and k = 6.2 X 10 7 exp — 14000/T s 1 (this last datum is a rate constant taken from L. D. Schmidt s The Engineering of Chemical Reactions (Oxford, 1997) for a reaction involving butadiene). Any spreadsheet program will immediately give a table of results such as ... 

A practical example of this reaction is given in Table 23-6 together with examples of related reactions known as the Curtins and Schmidt rearrangements. The latter two probably also involve rearrangement of an acyl nitrene, this time formed by decomposition of an acyl azide ... 

---