Ketones => alkyl halides

Oxathiane 101 is readily deprotonated using s-BuLi, and the resulting anion reacts with alkyl halides, ketones, and benzonitrile (85JOC657). The majority of work in this area, however, is due to Eliel and coworkers and has involved chiral 1,3-oxathianes as asymmetric acyl anion equivalents. In the earliest work it was demonstrated that the oxathianes 102 and 103, obtained in enantiomeri-cally pure form by a sequence involving resolution, could be deprotonated with butyllithium and added to benzaldehyde. The products were formed with poor selectivity at the new stereocenter, however, and oxidation followed by addition... 

Alcohols occupy a central position in organic chemistry. They can be prepared from many other kinds of compounds (alkenes.. alkyl halides, ketones, esters, and aldehydes, among others), and they can be transformed into an equally wide assortment of compounds (Figure 17.3). 

A gold monohydride species was also suggested in the report by Ito and Sawamura et al. on the dehydrogenative silylation of alcohols by HSiEt3 and a diphosphine gold(I) complex. Reaction was selective for the silylation of hydroxy groups in the presence of alkyl halides, ketones, aldehydes, alkenes, alkynes and other functional groups [193]. 

Table XXXVI is a list of some catalytic photochemical redox transformation of organic reactants by (Q or H)3PW 204o. In the presence of UV light, Q3PW12O40 reacts with paraffins, arenes, alcohols, alkyl halides, ketones, nitriles, thioethers, and water. Under either anaerobic or aerobic conditions, decarboxylation, dehydrogenation, dimerization, polymerization, oxidation, and acylation takes place.

Methylquinazolin-4(3i/)-one is converted into the dianion 1 using uncomplexed butyl-lithium. Subsequent condensations of 1 with alkyl halides, ketones and aldehydes result in selective modification of the original methyl group to form derivatives 2, This reaction represents a direct, general method for side-chain elaboration of 2-alkylquinazolin-4(3//)-ones. ... 

Reductive cleavage of imidazolidines 641 was implicated in the one-pot synthesis of N,N,N -trisubstituted ethylenediamines 643 from V,V -disubstituted ethylene diamines and an aldehyde R CHO. Presumably the intermediate iminium ion 642 is reduced by NaBH4 (Scheme 154) <2003SC3193>. Naphthalene-catalyzed lithiation of l,3-dimethyl-2-phenylimidazoline 644 leads to benzylic C-N bond cleavage. The intermediate dianion can be trapped with electrophiles (HjO, alkyl halides, ketones, and aldehydes) to afford diamines 645 <2005T3177>. 

Furthermore, over the past 15 years, it has also been demonstrated that titanium(m) complexes can be used as catalysts in organic transformations. Complexes containing a Ti(m) center have been shown to be active catalysts for the hydrosilylation of lactones, esters, and ketones and have also been used to reduce both aryl and alkyl halides, ketones, aldehydes, aromatic azo compounds, and epoxides. These organic applications of titanium(m) complexes are beyond the scope of this chapter. 

Tris(trimethylsilyl)silane (TTMSS) reducing agent for alkyl halides, ketones an alternative to tributyltin hydride. 

The activation of LiH by i-BuOH in the presence of Ni(OAc endows LiH with the power to reduce alkyl halides, ketones, alkenes, and sulfiirated compounds. The reagent can also effect coupling of aryl halides. ... 

The most general and well-developed procedures for the preparation of acetylenic ethers are based on dehydrohalogenation or dehalogenation of various haloacetals (for example, acetals of chloroacetaldehyde 52) or haloalkenyl ethers 53 (equation 34) . The first product in these eliminations usually is alkoxyacetylide 54 which can be subsequently quenched with a variety of electrophiles such as water, alkyl halides, ketones, etc to give the final product 55. 

Reaetions. Smia (or Ybla) in THF-CH3OH reduces a, 8-unsaturated acids and esters to saturated acids and esters in high yield. Of more interest, aldehydes are much more easily reduced than ketones so that selective reduction is possible. In the presence of an alkyl halide ketones undergo a Grignard-like reaction ... 

Using potassium phthalimide, sodium azide, or ammonia together with suitable alkyl halides, ketones, or aldehydes, it is possible to generate a large variety of primary, secondary, and tertiary amines as well as quaternary ammonium salts. Let s get some practice using these methods to prepare amines. 

---