1530-33-2Relevant articles and documents
Photocycloaddition of biscyclopropyl alkenes to C60: An unprecedented approach toward cis-1 tricyclic-fused fullerenes
Tzirakis, Manolis D.,Alberti, Mariza N.,Orfanopoulos, Michael
, p. 3364 - 3367 (2011)
A novel, simple, and entirely regioselective tandem cycloaddition of biscyclopropyl-substituted alkenes to [60]fullerene has been revealed. This reaction affords cis-1 tricyclic-fused organofullerenes bearing the hitherto elusive 5-4-5 fused tricyclic ring system.
Remote sp3 C–H Amination of Alkenes with Nitroarenes
Xiao, Jichao,He, Yuli,Ye, Feng,Zhu, Shaolin
supporting information, p. 1645 - 1657 (2018/05/16)
Direct installation of a functional group at remote, unfunctionalized sites in an alkyl chain is a synthetically valuable but rarely reported process. The remote relay hydroarylamination of distal and proximal olefins, and of olefin isomeric mixtures, has been achieved through NiH-catalyzed alkene isomerization and sequential reductive hydroarylamination with nitroarenes. This provides an attractive approach to the direct installation of a distal arylamino group within alkyl chains. The single-step conversion of simple olefins and nitro(hetero)arenes to value-added arylamines is a practical strategy for amine synthesis as well as the remote activation of sp3 C–H bonds. The value of this transformation is further supported by the regioconvergent arylamination of isomeric mixtures of olefins. Modern organic synthesis requires more efficient strategies, such as C–H functionalization, with which to construct complex molecules from readily available chemicals. Undirected functionalization of remote aliphatic C–H bonds is a synthetically valuable but largely unknown process. Synergistic combination of metal-catalyzed chainwalking (migration of a double bond along the hydrocarbon chain, a process involving repeated migratory insertions and β-hydride eliminations) and cross-coupling chemistry offers a general approach to the remote functionalization of easily accessed unsaturated hydrocarbon substrates. In this paper, we demonstrate that direct installation of a distal arylamino group can be achieved from two common feedstock chemicals (olefins and nitroarenes) via nickel hydride chemistry. It is anticipated that the strategy could inspire the development of other remote functionalizations with different regioselectivity as well as asymmetric transformations. Zhu and colleagues describe the remote hydroamination of alkenes with nitro(hetero)arenes through nickel-catalyzed alkene isomerization and sequential reductive relay hydroamination process. Using two common feedstock chemicals, olefins and nitroaromatics, in an operationally simple procedure, this attractive protocol provides efficient and practical access to a wide range of arylamines under mild conditions.
A modular synthesis of teraryl-based α-helix mimetics, part 1: Synthesis of core fragments with two electronically differentiated leaving groups
Peters, Martin,Trobe, Melanie,Tan, Hao,Kleineweischede, Rolf,Breinbauer, Rolf
supporting information, p. 2442 - 2449 (2013/04/24)
Teraryl-based α-helix mimetics have proven to be useful compounds for the inhibition of protein-protein interactions (PPI). We have developed a modular and flexible approach for the synthesis of teraryl-based α-helix mimetics. Central to our strategy is the use of a benzene core unit featuring two leaving groups of differentiated reactivity in the Pd-catalyzed cross-coupling used for terphenyl assembly. With the halogen/diazonium route and the halogen/triflate route, two strategies have successfully been established. The synthesis of core building blocks with aliphatic (Ala, Val, Leu, Ile), aromatic (Phe), polar (Cys, Lys), hydrophilic (Ser, Gln), and acidic (Glu) amino acid side chains are reported. Turn on: Teraryl-based α-helix mimetics can be effectively produced by sequential Suzuki coupling of a central core fragment featuring electronically differentiated leaving groups with aryl boronic pinacol esters (see scheme; dppf=1,1′-bis(diphenylphosphino) ferrocene, DME=dimethoxyethane, Pin=pinacol, Tf=trifluoromethanesulfonyl). With a set of only 2×18 building blocks, all permutations of α-helix mimetics can be produced. Copyright
