TY - JOUR
T1 - A Unified Synthesis of Electron-Deficient 1,4- and 1,1,4-Substituted 1,3-Dienes through a Base-Promoted Allylation Followed by Retro-Michael Vinylogous Dehydrosulfinylation
AU - Rothstein, Ayelet
AU - Trifonov, Lena
AU - Keidar, Niv
AU - Afri, Michal
AU - Korshin, Edward E.
AU - Gruzman, Arie
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/10/11
Y1 - 2024/10/11
N2 - We disclose a general 2-step synthesis of electron-poor 1,4- and 1,1,4-substituted buta-1,3-dienes bearing electron-withdrawing substituents at both termini of the conjugated system. The method relies on a base-promoted C-allylation of primary or secondary alkylsulfones with γ-bromocrotonate or related amide, nitrile, or sulfone and subsequent vinylogous retro-Michael dehydrosulfinylation. The geometry of the resulting dienes is substrate-dependent, and predominantly E,E-dienes are formed from E-electrophiles. This phosphorus- and transition-metal-free method tolerates a variety of functionalities and could serve as a supplement to Wittig, HWE, and Julia olefinations.
AB - We disclose a general 2-step synthesis of electron-poor 1,4- and 1,1,4-substituted buta-1,3-dienes bearing electron-withdrawing substituents at both termini of the conjugated system. The method relies on a base-promoted C-allylation of primary or secondary alkylsulfones with γ-bromocrotonate or related amide, nitrile, or sulfone and subsequent vinylogous retro-Michael dehydrosulfinylation. The geometry of the resulting dienes is substrate-dependent, and predominantly E,E-dienes are formed from E-electrophiles. This phosphorus- and transition-metal-free method tolerates a variety of functionalities and could serve as a supplement to Wittig, HWE, and Julia olefinations.
UR - http://www.scopus.com/inward/record.url?scp=85205728239&partnerID=8YFLogxK
U2 - 10.1021/acs.orglett.4c03189
DO - 10.1021/acs.orglett.4c03189
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C2 - 39356088
AN - SCOPUS:85205728239
SN - 1523-7060
VL - 26
SP - 8565
EP - 8571
JO - Organic Letters
JF - Organic Letters
IS - 40
ER -