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1.5.2.1.4 Prins–Pinacol Rearrangement

DOI: 10.1055/sos-SD-219-00174

Wang, S.-H.; Tu, Y.-Q.; Tang, M.Science of Synthesis: Applications of Domino Transformations in Organic Synthesis, (20151277.

The Overman group has developed an outstanding sequential series of acid-catalyzed cationic cyclization–rearrangements, which have been used to synthesize stereochemically complex substituted pyrrolidines,[‌18‌‌20‌] substituted tetrahydrofurans,[‌21‌‌24‌] and carbocyclic rings.[‌25‌,‌26‌] As a potentially useful annulation sequence, when cyclic substrates of type 26 are used, the rearrangements result in an unusual reaction in which elaboration of a new five-membered ring is coupled with a one-carbon ring enlargement of the starting carbocyclic ring (Scheme 8).

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Meeee 8 Meee-Meeeeeeee Meeeeeeeeeeeeee Meeeeeeeeee ee Meeee Meeeeee[‌88‌]

Meeee Meeeeeeee Meeeeee Meeee (%) Mee
8 88 [‌88‌]
8 88 [‌88‌]
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Meeee 8 Meeeeeeeeeeeeeee Meeeeeeeeeee ee Meeeeeeeeee Meeee ee Meeeeeeeee Meeeeeee Meeeeeeeeee–Meeeeee Meeeeeeeeeeeee[‌88‌]

Meeee Meeeeeeee Meeeeee ee Meeee (%) Mee
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Meeeee 88 Meeeeeeeeeeeeeee Meeee Meeeeeeee ee (−)-Meeeeeeeeee eee (+)-Meeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M*,8eM*,8eM*)-8-Meeeeeeeeeeeeee-8M-eeeeeeeeee[e]eeeee-8-eee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

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Meeee Meeeeeeeeeeee 88 (e = 8–8); Meeeeee Meeeeeeee:[‌88‌]

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References