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Catalytic Intramolecular Coupling of Ketoalkenes by Allylic C( sp 3 )−H Bond Cleavage: Synthesis of Five‐ and Six‐Membered Carbocyclic Compounds
Author(s) -
Mita Tsuyoshi,
Uchiyama Masashi,
Sato Yoshihiro
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201901533
Subject(s) - chemistry , intramolecular force , allylic rearrangement , xantphos , bond cleavage , catalysis , medicinal chemistry , stereochemistry , cleavage (geology) , intramolecular reaction , organic chemistry , palladium , geotechnical engineering , fracture (geology) , engineering
In the presence of a catalytic amount of cobalt(II) acetylacetonate/Xantphos in combination with trimethylaluminum, various ketoalkenes underwent an intramolecular cyclization reaction triggered by cleavage of the allylic C( sp 3 )−H bond, affording carbocyclic compounds with high regio‐ and diastereoselectivity. Mono‐, bi‐, and tricarbocyclic compounds were produced in good yields. One of the products thus obtained was derivatized into tramadol in four simple steps. Notably, these intramolecular cyclizations took place in the absence of a gem ‐disubstituent on the tethered carbon chain (without the Thorpe‐Ingold effect).