Enantioselective alkene radical cations reactions

Reaction mechanisms : Part (i) Radical and radical ion reactions

“…89 Finally, Wright used radical cation cyclizations onto furans and thiophenes for the synthesis of annulated heterocycles. 90 For radical cations, incorporation of a pendant nucleophile can lead to cyclization via a polar process, as is illustrated by recent results reported by Crich 91 and Roth (Scheme 27). 92 The example cited in Scheme 27 also provides a good example of how a series of sequential rearrangements can be used as a tool for organic synthesis.…”

Acid‐Catalysed or Radical‐Promoted Allylic Substitution of 2‐Methylene‐2,3‐dihydrobenzofuran‐3‐ols with Thiol Derivatives: a Novel and Expedient Synthesis of 2‐(Thiomethyl)benzofurans

“…Direct fragmentation of II to give 3 and the hydroxyl radical HO · appears unlikely in view of the high instability of the latter species 6. Alternatively, intermediate II can undergo ionic fragmentation with elimination of HO – and formation of a radical cation species III 7,8. Deprotonation of the latter by HO – can then afford the stabilized radical species IV .…”

Allylic azides: synthesis, reactivity, and the Winstein rearrangement

“…148,149 Other reactions using allyl azide are known, but will not be discussed further. [150][151][152][153][154][155][156] It is worth noting that low molecular weight azides, such as this one, are potentially explosive. 157 Organic azides with a carbon to nitrogen ratio greater than 3 to 1 are generally safer to handle.…”