Amines, alkene radical cations

In an extensive investigation of the stereochemical memory effect, a series of six diastereomeric pairs of substrates was prepared to probe the effect of single, then multiple substituents on the 5-exo cyclization of amines onto alkene radical cations [144,145]. Overall, these cyclizations were highly dia-stereoselective and were accounted for by a transition-state model employing a chairlike transition state with attack of the nucleophilic amine on the opposite face of the alkene radical to the one shielded by the phosphate anion in the initial contact ion pair (Scheme 34), as exemplified in Schemes 35 and 36. 

Enantioselective synthesis of 2-substituted piperidines with 60% ee has been reported via radical precursors being trapped in an intramolecular reaction (Scheme 17) <2003OL3767>. These cyclizations were rationalized in terms of chair-like transition states, with the maximum number of pseudoequatorial substituents, in which the nucleophilic amine attacks the alkene radical cation on the face opposite to the phosphate anion. 

As was noted in Scheme 12, distonic radical cations obtained from cyclopropane bond cleavages add oxygen rapidly, producing products with two CO bonds. So do some alkene radical cations. Addition of O2 to an alkene radical cation is formally a nucleophilic attack by the single alkene n electron on O2, and oxidizes both carbon atoms (an alkene radical cations has formally two -f carbons, and the adduct a 1+ and an oxygen-bound carbon). The oxygenation of the radical cation of bia-damantylidine (96) leads to dioxetanes such as 98 in chain reactions (see Scheme 21) [110]. The reactions may be initiated electrochemically or photochemically, but tris(o,p-dibromophenyl)amine hexafluoroantimonate, 97, is a superior catalyst for the dark reaction of certain tetraalkylalkenes, with turnovers up to ca. 800 at... 

The photoinduced anti-Markovnikov addition of methanol to 1,1-diphenylethene reported by Arnold and co-workers in 1973 provides the first example of the addition of a nucleophile to an arylalkene radical cation. There are now a number of studies that demonstrate the generality of nucleophilic addition of alcohols, amines, and anions such as cyanide to aryl- and diaryl-alkene radical cations. Product studies and mechanistic work have established that addition occurs at the 3-position of I-aryl or 1,1 -diarylalkene radical cations to give arylmethyl or diaryl-methyl radical-derived products as shown in Scheme I for the addition of methanol to 1,1-diphenylethene. For neutral nucleophiles, such as alcohols and amines, radical formation requires prior deprotonation of the 1,3-distonic radical cation formed in the initial addition reaction. The final product usually results from reduction of the radical by the sensitizer radical anion to give an anion that is then protonated, although other radical... 

As mentioned above, triplet Cgo is readily photoreduced by amines and other donors to Cgo radical anion and the donor radical cations [64], We expected this reaction to lead to adducts with covalent bonds. Such adducts are formed with some amines in ground state chemistry [33, 60, 83], but the photochemical process should be more selective and easily controlled, since only one-electron reduction is possible in the photochemical process. C o in the Si state has been suggested to produce an exciplex with triethylamine which seems to react with ground-state Cgo to give a stable product [117]. The reduction potential of the triplet is high enough that electron-transfer from many donors such as electron-rich aromatics and alkenes should be possible. 

Simple amines in the presence of Oxone oxidize alkenes to oxiranes. For example, Oxone, pyridine, and a 2-pyrrolidine derivative in a medium of aqueous acetonitrile selectively converts the triene in Equation (72) to a single epoxide. This process also proceeds using noncyclic alkenes. The mechanism is believed to proceed via a single-electron transfer (SET) process involving radical cation intermediates <2000JA8317>. 

Products of addition to styrene double bonds can arise as a result of light induced electron transfer reactions. Lewis has studied the intramolecular reaction of l-phenyl-w-amino alkenes (422) 289,290 products arise from electron transfer from the amine nitrogen to the excited state of the styryl group followed by intramolecular proton transfer in the radical ion pair produced. The resultant biradical then couples to yield the isolated products (423) and (424). Sensitisation of the intermolecular analogue of this reaction by 1,4-dicyanobenzene has been reported and is proposed to occur by electron transfer from the styrene to the excited state of the sensitiser followed by attack of an amine on the styrene radical cation. This ultimately leads to the product of anti-Markovnikov addition of the amine across the double bond of the styrene. This is similar to the sequence long since established by... 

A variety of aryl and diarylalkene radical cations have been generated in solution and characterized using transient absorption spectroscopy. Many of these are sufficiently long-lived for detailed kinetic studies of their intermolecular reactivity under conditions that are comparable to those used in mechanistic and synthetic studies. Reactions with nucleophiles typically occur by either addition or electron transfer, with the latter dominating in cases where the oxidation potential of the nucleophile is lower than that of the alkene. The data summarized herein indicate that most arylalkene radical cations are unseleclive in their additions to anionic nucleophiles in nonprotic solvents. By contrast, the additions to neutral nucleophiles such as alcohols and amines cover a range of timescales and clearly demonstrate the... 

As already indicated, carbonyl compounds such as ketones, aldehydes, enones, and quinones possess the property to act as effective electron acceptors in the excited state for generating radical anions in the presence of electron-donating partners such as alkenes, aromatics, ruthenium complexes, amines, and alcohols. We will not consider the reactivity of enones and quinones, but we will focus our attention on the behavior of the radical anions formed from ketones and aldehydes. Four different processes can occur from these radical anions including coupling of two radical anions and/or coupling of the radical anion with the radical cation formed from the donor, abstraction of hydrogen from the reaction media to produce alcohols, cyclization, in the case of ce-unsaturated radical anions, and fragmentation when a C -X bond (X=0, C) is present (Scheme 18). 

Cyclic Amines Similar to cycloketones [reaction (6.43)], the first step in the fragmentation of ionized cyclic amines is a-cleavage of the C—C bond next to the C—N bond to produce a distonic ion [20]. Subsequent fragmentation proceeds via the loss of an alkene molecule or via an H-transfer followed by the loss of an alkyl radical. A typical example of the latter fragmentation is the loss of an ethyl radical from the cyclopentylamine radical cation. Ionized cyclic amines also exhibit an abundant (M - 1) ion from loss of the a-H (see Figure 6.8). As exemplified for piperidine, cyclic amines also participate in these generic fragmentation reactions of heterocyclic compounds [reaction (6.42)]. 

The DCNB-sensitized addition reactions of 1,1-diarylethylenes with ammonia or primary amines yield the a ri-Markovnikov adducts. The mechanism is analogous to that shown in Scheme 7 for addition to sthbene. The regioselectivity is determined by nucleophilic attack of the amine on the alkene cation radical to yield the more stable benzyl radical intermediate. The mechanism and dynamics of the reactions of p-methoxystyryl radical cations with amines have been investigated. Anihne and EtjN are found to react as electron donors with rate constants near the diffusional Hmit. Primary amines react as nucleophiles, with somewhat slower rate constants. 

---