118362-75-7Relevant articles and documents
Connecting remote C–H bond functionalization and decarboxylative coupling using simple amines
de Azambuja, Francisco,Yang, Ming-Hsiu,Feoktistova, Taisiia,Selvaraju, Manikandan,Brueckner, Alexander C.,Grove, Markas A.,Koley, Suvajit,Cheong, Paul Ha-Yeon,Altman, Ryan A.
, p. 489 - 496 (2020)
Transition metal-catalysed C–H functionalization and decarboxylative coupling are two of the most notable synthetic strategies developed in the past 30 years. Here, we connect these two reaction pathways using bases and a simple Pd-based catalyst system to promote a para-selective C–H functionalization reaction from benzylic electrophiles. Experimental and computational mechanistic studies suggest a pathway that involves an uncommon Pd-catalysed dearomatization of the benzyl moiety followed by a base-enabled rearomatization through a formal 1,5-hydrogen migration. This reaction complements ‘C–H activation’ strategies that convert inert C–H bonds into C–metal bonds prior to C–C bond formation. Instead, this reaction exploits an inverted sequence and promotes C–C bond formation prior to deprotonation. These studies provide an opportunity to develop general para-selective C–H functionalization reactions from benzylic electrophiles and show how new reactive modalities may be accessed with careful control of the reaction conditions. [Figure not available: see fulltext.].
Asymmetric Hydroacylation Involving Alkene Isomerization for the Construction of C3-Chirogenic Center
Liu, Chong,Yuan, Jing,Zhang, Zhenfeng,Gridnev, Ilya D.,Zhang, Wanbin
supporting information, p. 8997 - 9002 (2021/03/16)
A new transformation pattern for enantioselective intramolecular hydroacylation has been developed involving an alkene isomerization strategy. Proceeding through a five-membered rhodacycle intermediate, 3-enals were converted to C3- or C3,C5-chirogenic cyclopentanones with satisfactory yields, diastereoselectivities, and enantioselectivities. A catalytic cycle has been theoretically calculated and the origin of the stereoselection is rationally explained.
Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles
Malapit, Christian A.,Caldwell, Donald R.,Luvaga, Irungu K.,Reeves, Jonathan T.,Volchkov, Ivan,Gonnella, Nina C.,Han, Zhengxu S.,Busacca, Carl A.,Howell, Amy R.,Senanayake, Chris H.
supporting information, p. 6999 - 7002 (2017/06/06)
β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.
