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Cobalt Catalyzed Reductive Spirocyclopropanation Reactions
Author(s) -
Werth Jacob,
Berger Kristen,
Uyeda Christopher
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.201901293
Subject(s) - chemistry , intramolecular force , cobalt , catalysis , cycloaddition , carbene , pyridine , diimine , hydride , reductive elimination , sulfur , photochemistry , combinatorial chemistry , medicinal chemistry , hydrogen , organic chemistry
Cobalt pyridine−diimine (PDI) complexes catalyze the reductive spirocyclopropanation of terminal 1,3‐dienes. gem ‐Dichlorocycloalkanes serve as carbene precursors and Zn is used as a terminal electron source. The reaction is effective for a range of gem ‐dichloro partners including those containing sulfur and nitrogen heterocycles. An example of an intramolecular Rh‐catalyzed [5+2]‐cycloaddition of a vinyl spirocyclopropane is demonstrated, providing rapid access to a complex tricyclic framework. Overall, this catalyst system is capable of suppressing the kinetically facile 1,2‐hydride shift, which has hampered the development of Simmons−Smith reactions using Zn carbenoids possessing β‐hydrogen atoms.