Alkenyl halides alcoholic groups

Allyiic halides, alcohols, ethers, acetates, lactones, phosphates, epoxides, sulfides, sulfonium salts, se-lenides and ammonium salts undergo transition metal catalyzed coupling reactions with C(sp )—Li, —Mg, —B, —Al, —Sn, —Zt, —Cd and — Hg reagents. Table 1 summarizes the allyiic leaving groups, alkenyl and aryl metallic reagents, catalytically active metals and references and Table 2 the regio- and stereo-chemical aspects. 

Table 7.13 contains a short list of the almost limitless number of (variable) E2 reactions from which examples might be provided. Indeed, although the table holds only alkyl and alkenyl halides, in concert with the substance of this chapter, the nature of the leaving group can be altered to include derivatives of such common functional groups as alcohols (Chapter 8), thiols (Chapter 8), and amines (Chapter 10). As more work is done, the list grows. 

Some authors have described the generation of boronates and stannanes bound to a support starting from the corresponding aryl haHdes [372, 6]. Boranes, boronic esters, and stannanes can furthermore be readily obtained from vinyl halides or from alkenes or alkynes by means of hydroboration or hydrostannylation (see Section 4.2). Boronates and silanes or stannanes can act as carbanion equivalents. Thus, support-bound boronates can release aryl alkenyl groups upon transmetala-tion to Rh. The intermediately formed Rh species can act as nucleophiles, and react with aldehydes to give alcohols (618) or can perform Michael additions (621, 622) [437, 438, 439] (Scheme 129) (see also Sections 4.7.15 and 4.2). 

As was the case for alkenyl and aryl halides (Chapter 7), SnI and Sn2 (or SNl-like and SN2-like) reactions do not appear to take place for enols and phenols either. However, along with addition-elimination processes, which occur with enols and phenols as with halides (e.g., see Chapter 7, Figure 7.11), truly exceptional leaving groups can be created from simple enols and phenols by forming suitable derivatives (as is the case with alcohols). Further, there is some evidence that actual SnI (or SnI like) processes to form vinyl cations (R2C=CR" ) may occur from such derivatives ... 

Copper(I)/TEMPO/NMI-catalyzed Aerobic Oxidation of Alcohols. A novel (bpy)Cu(I)/TEMPO/NMI system has been developed to achieve aerobic oxidation of 1° alcohols and avoid overoxidation. This system gave improved conversion relative to other aerobic oxidation protocols, demonstrating functional group tolerance for a diverse range of substrates bearing aliphatic, aryl, alkenyl, alkynyl, halides, as well as 0-, N-, and 5 -heteroatoms (eq 28). In the presence of unprotected 2° alcohols, 1° alcohols undergo selective oxidation (eq 29). ... 

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