In:
Angewandte Chemie, Wiley, Vol. 134, No. 32 ( 2022-08-08)
Abstract:
1,3‐Allyl and 1,2‐allyl shifts through [3,3]‐ and [2,3] ‐sigmatropic rearrangements are well‐established and widely used in organic synthesis. In contrast, 1,5‐allyl shift through related [3,5]‐sigmatropic rearrangement is unknown because [3,5] ‐sigmatropic rearrangement is thermally Woodward–Hoffmann forbidden. Herein, we report an unexpected discovery of a formal 1,5‐allyl shift of allyl furfuryl alcohol through a 2‐step sequential rearrangement. Mechanistically, this formal 1,5‐allyl shift is achieved through a sequential ring expansion/contraction rearrangement: 1) Achmatowicz rearrangement (ring expansion), and 2) cascade oxonia‐Cope rearrangement/retro‐Achmatowicz rearrangement (ring contraction). This new 1,5‐allyl shift method is demonstrated with 〉 20 examples and expected to find applications in organic synthesis and materials chemistry.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.32
DOI:
10.1002/ange.202205919
Language:
English
Publisher:
Wiley
Publication Date:
2022
detail.hit.zdb_id:
505868-5
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
514305-6
detail.hit.zdb_id:
505872-7
detail.hit.zdb_id:
1479266-7
detail.hit.zdb_id:
505867-3
detail.hit.zdb_id:
506259-7
Permalink