Reduction reactions alkyl halides

Stabilization of intermediates by strong adsorption will frequently be a necessary precondition for synthesis. Thus, in the case of the Kolbe reaction, further oxidation of the radicals is prevented the formation of metal-carbon bonds in the reduction of alkyl halides (Fleischmann et al., 1971a Galli and Olivani, 1970) or oxidation of Grignard reagents (Fleischmann et al., 1972c) is shown by the isolation of organometallic... 

The tin hydrides find important applications as reducing agents. Many of their reactions (particularly the reduction of alkyl halides and the hydrostannation of simple alkenes and alkynes) arc known to proceed through RaSn- intermediates, and this aspect of their chemistry is referred to in Section II,G. 

The reaction is a reduction of alkyl halide zinc atoms transfer electrons to the carbon atom of the alkyl halide. 

This is the basic reaction of the commercial Nalco process. On the other hand, reduction of alkyl halides at the cathode is often described in general terms as ... 

Neither reaction excludes the other, nor are these the only routes possible. The oxidation of alkylanions on a metallic anode is likely. Other processes are more clearly indicated when, instead of Cd, Zn is used as a cathode. In the latter case, zinc alkyls R2Zn and RZnI are formed by cathodic reaction of RI. This allows an efficient preparation of R4M where M = Pb, Sn and R = propyl, butyl or pentyl39, in contrast to the cathodic reduction of alkyl halides which is practically limited to the methyl and ethyl groups. 

Although the tin hydride reductions of alkyl halides seem simple, one must be careful because these reactions occur by a free radical mechanism. This is important, because the carbon radical produced in the reaction can isomerize68,78 and one often obtains two different stereoisomers from the synthesis. Another problem is that chiral centres can be lost in tin hydride reductions when an optically active halide is reduced. One example of this is the reduction of benzyl-6-isocyanopenicillanate with tributyltin deuteride78 (Scheme 14). The amount of isomerization depends on the temperature, the concentration of the tin hydride and the presence of and /-substituents78-82. However, some authors have reported tin hydride reductions where no racemization was observed78. 

Fig. 5 Marcus plot of electron transfer reductions of alkyl halides, as contrasted with archetypal SN2 substitution processes (Finkelstein reactions, circled see Eberson,...

The reaction of thiyl radicals with silicon hydrides (Reaction 3.18) is the key step of the so called polarity-reversal catalysis in the radical-chain reduction of alkyl halides as well as in the hydrosilylation of olefins using silane-thiol couple (see Sections 4.5 and 5.1) [33]. The reaction is strongly endothermic and reversible (Reaction —3.18). 

As a last point, it should be mentioned that cobalt(II) salen (26) and cobalt(II) salophen (27) are known to interact with molecular oxygen in solution. Dioxygen forms a peroxo bridge between two cobalt centers, resulting in an often-undesired dicobalt(III) species that can attenuate the efficiency of electrogenerated cobalt(I) salen or cobalt(I) salophen for other reactions of interest, for example, the catalytic reduction of alkyl halides discussed in the following text. 

Several research groups ha ve been involved in the study of ET reactions from an electrochemically generated aromatic radical anion to alkyl halides in order to describe the dichotomy between ET and polar substitution (SN2). The mechanism for indirect reduction of alkyl halides by aromatic mediators has been described in several papers. For all aliphatic alkyl halides and most benzylic halides the cleavage of the carbon-halogen bond takes place concertedly with the... 

The first reaction provides a route for the reduction of alkyl halides since the carbo-cation (isopropyl, in Rl) may be prepared from action of AICI3 on the corresponding alkyl halide. Reactions of the type Rl are also important in the process, catalytic cracking, in the manufacture of gasoline. They have also been studied in mass spectro-metric experiments [235]. Reaction R2 is one route to the preparation of carbocations under stable ion conditions. Reaction R3 is employed in the laboratory synthesis of the tropylium cation. Reaction R4, the (crossed) Cannizzaro reaction, is unusual in that it takes place under strongly basic conditions. The oxy dianion is an intermediate in the reaction of concentrated hydroxide with the aldehyde, R HO. None of R1, R2, or R3 may have hydrogen atoms a to the carbonyl groups. Formaldehyde (R1 = H) is readily... 

Alkylnickel formation has also been extensively studied in the one-electron reductions of alkyl halides and peroxides by a nickel(I) macrocycle (189, 196, 197). Although two forms of the nickel(II) isomers of the tetra-N-methylated macrocycle are known, there is no ready interconversion between the [(f ,f ,S,S,)Nin(tmc)]2+ and [(i ,S,S,/ )]Ni"(tmc)]2+. Solutions of the [Ni (tmc)]+ complexes can be prepared in alkaline media (183), although within several Hours isomerization of the nickel(I) forms takes place. The complexes are again strong reductants (E° = — 0.90 V). Using the lft,4ft,8S,llS isomer (Fig. 12), Espenson and his co-workers have examined reactions with a variety of primary alkyl halides (189). For most systems studied, the overall reactions exhibit the stoichiometry according to Eq. (20) ... 

To utilize the strong reducing power of the 3(da po) excited states of the platinum and iridium dimers, the nonproductive back electron transfer reactions need to be inhibited. An effective way to accomplish this is to use acceptors that are thermally unstable after the initial electron transfer. Reduction of alkyl halides has been shown to lead to short-lived radical anions RXT, which rapidly decompose to give R- and X (k... 

Radical reductions of alkyl halides in water.1 Radical reactions with Bu3SnH are limited to organic solvents, but this tin hydride (1) is sufficiently soluble in water to reduce alkyl bromides or iodides under free-radical conditions in water or in organic solvents. 

The metal-centered reduction of iron and cobalt porphyrins [(por)Afn] yields metalloporphyrin anions [Eq. (13.13)]. The reduction potential for this reaction is 13, and is equivalent to the N- value for the oxidation of the metal-centered nucleophile [(por)uM-]. The one-electron reduction of alkyl halides yields the... 

The reduction of alkyl halides to organometallic compounds in aprotic solvents involves a heterogeneous reaction on the metal surface. This metal surface must be pure metal if it is to react efficiently in the desired way. If the surface of the metal has reacted with oxygen (Li, Mg, Zn) or even with nitrogen (Li), one must first remove the metal oxide or lithium nitride layer. This can be accomplished in the following ways ... 

The radical intermediates from Cr(II) reduction of alkyl halides can in principle be used synthetically, but have only seen limited attention to this point. co-Haloalkynes (bromides, iodides), in the presence of excess Cr(C104)2, undergo cyclization reactions to form exo-alkylidene cycloalkanes (equation 176)347. These reactions proceed by the radical cyclization of intermediate 42 onto the alkyne unit, which undergoes subsequent reduction by Cr(II) to give a hydrolytically unstable vinylchromium(III). Rings of four, five and six members can be formed. Alternatively, a-iodo esters undergo intramolecular atom transfer radical cyclizations onto alkynes or alkenes with catalytic or stoichiometric amounts of... 

Key to designing reactions using Sml2 or SmI2-HMPA is a fundamental understanding of the rates of reaction pathways and the seminal work of Curran is fundamentally important in this regard. Curran s detailed study of the reduction of alkyl halides provided rate constants for the reduction of primary, secondary and tertiary radicals with SmI2-HMPA (Scheme 3.3).2,5... 

The ability of Sml2 to reduce alkyl halides has been exploited in a number of carbon carbon bond-forming reactions. Radicals generated from the reduction of alkyl halides can be trapped by alkenes in cyclisation reactions to form carbocyclic and heterocyclic rings (see Chapter 5, Section 5.3), and the alkyl-samarium intermediates can be used in intermolecular and intramolecular Barbier and Grignard reactions (see Chapter 5, Section 5.4). The reduction of ot-halocarbonyl compounds with Sml2 gives rise to Sm(III) enolates that can be exploited in Reformatsky reactions (Chapter 5, Section 5.5) and are discussed in Section 4.5. 

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