- One-Pot Synthesis of Metastable 2,5-Dihydrooxepines through Retro-Claisen Rearrangements: Method and Applications
-
A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time.
- Zhang, Wei,Baudouin, Emmanuel,Cordier, Marie,Frison, Gilles,Nay, Bastien
-
supporting information
p. 8643 - 8648
(2019/07/16)
-
- A new preparation of 2,5-dihydro-1-benzoxepins using Mitsunobu cyclization, and the synthesis of natural radulanins
-
Mitsunobu cyclization of o-[4-hydroxy-3-methyl-2(Z)-butenyl]phenol 2a effected selective seven-membered cyclization to give 3-methyl-2,5-dihydro-1- benoxepin 1a. Using this procedure, natural radulanin A and radulanin A methyl ether were synthesized effec
- Yamaguchi, Seiji,Furihata, Katsunori,Miyazawa, Masahiro,Yokoyama, Hajime,Hirai, Yoshiro
-
p. 4787 - 4790
(2007/10/03)
-