35237-29-7Relevant academic research and scientific papers
Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling
Derosa, Joseph,Tran, Van T.,Boulous, Mark N.,Chen, Jason S.,Engle, Keary M.
, p. 10657 - 10660 (2017)
A nickel-catalyzed conjunctive cross-coupling between non-conjugated alkenes, aryl iodides, and alkylzinc reagents is reported. Excellent regiocontrol is achieved utilizing an 8-aminoquinoline directing group that can be readily cleaved to unmask net β,γ-dicarbofunctionalized carboxylic acid products. Under optimized conditions, both terminal and internal alkene substrates provided the corresponding alkyl/aryl difunctionalized products in moderate to excellent yields. The methodology developed herein represents the first three-component 1,2-dicarbofunctionalization of non-conjugated alkenes involving a C(sp3)-C(sp3) reductive elimination step.
Harnessing Secondary Coordination Sphere Interactions That Enable the Selective Amidation of Benzylic C-H Bonds
Jung, Hoimin,Schrader, Malte,Kim, Dongwook,Baik, Mu-Hyun,Park, Yoonsu,Chang, Sukbok
, p. 15356 - 15366 (2019/10/22)
Engineering site-selectivity is highly desirable especially in C-H functionalization reactions. We report a new catalyst platform that is highly selective for the amidation of benzylic C-H bonds controlled by π-πinteractions in the secondary coordination sphere. Mechanistic understanding of the previously developed iridium catalysts that showed poor regioselectivity gave rise to the recognition that the π-cloud of an aromatic fragment on the substrate can act as a formal directing group through an attractive noncovalent interaction with the bidentate ligand of the catalyst. On the basis of this mechanism-driven strategy, we developed a cationic (ν5-C5H5)Ru(II) catalyst with a neutral polypyridyl ligand to obtain record-setting benzylic selectivity in an intramolecular C-H lactamization in the presence of tertiary C-H bonds at the same distance. Experimental and computational techniques were integrated to identify the origin of this unprecedented benzylic selectivity, and robust linear free energy relationship between solvent polarity index and the measured site-selectivity was found to clearly corroborate that the solvophobic effect drives the selectivity. Generality of the reaction scope and applicability toward versatile γ-lactam synthesis were demonstrated.
Zirconocene-catalyzed sequential ethylcarboxylation of alkenes using ethylmagnesium chloride and carbon dioxide
Shao, Peng,Wang, Sheng,Chen, Chao,Xi, Chanjuan
supporting information, p. 6640 - 6642 (2015/04/14)
The zirconocene-catalyzed sequential ethylcarboxylation of alkenes using ethylmagnesium chloride and carbon dioxide has been developed. A range of alkenes were transformed into the corresponding carboxylic acids in high yields.
