Protecting groups, avoidance

The major problems with industrial-scale applications of this procedure are the use of expensive reagents, the required chromatographic separation of the side products and the competitive formation of oxazolines. The use of carbamate protecting groups avoided the oxazoline problem and is usually preferred, since the resulting protected 3-amino-substituted /3-lactams 150 can later be deprotected and reacylated. 

Synthesis of large heterocycles usually involves condensation reactions of two difunctional molecules. Such molecules tend to polymerize. So far two special techniques have been described above to avoid this important side-reaaion , namely high dilution and use of templates. The general procedure to avoid polymerizations in reactions between difunctional molecules is, of course, the application of protecting groups as described in sections 4.1.2 and 2.6. 

Diphenylmethyl, substituted 5-diphenylmethyl, and 5-triphenylmethyl thioethers have often been formed or cleaved by the same conditions, although sometimes in rather different yields. As an effort has been made to avoid repetition in the sections that describe these three protective groups, the reader should glance at all the sections. 

Hg(OAc)2, H2O, 80% AcOH, HSCH2CH2SH, 25°, 5-20 min H2S, 2 h, high yield. The removal of an 5-benzylthiomethyl protective group from a dithioacetal with mercuiy(II) acetate avoids certain side reactions that occur when an 5-benzyl thioether is cleaved with sodium/ammonia. The dithioacetal is stable to hydrogen bromide/acetic acid used to cleave benzyl carbamates. 

Minimize derivatives. Syntheses should be designed with minimal use of protecting groups to avoid extra steps and reduce waste. 

The use of diamine 27, bearing a fluorous-Boc protecting group, has been used with microwave irradiation in an Ugi/de-Boc/cyclization strategy for the synthesis of benzimidazoles 28 and quinoxalinones 29 [64]. Compared to the original procedures, which take 1-2 days, this approach avoids the use of... 

The cyclic kotal (19) was again used as protection and the methane sulphonyl (MeSOg or Ms, mesylate) group was used as the leaving group X (p T2S) (20). The protecting group was left in until the end to avoid any side reactions. 

Indicate one or more satisfactory oxidants for effecting the following transformations. Each molecule poses issues of selectivity or the need to preserve a sensitive functional group. Select oxidants that can avoid the installation of protecting groups. In most cases, a one-pot reaction is possible, and in no case is a sequence of more than three steps required. Explain the reason for your choice of reagent(s). 

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