3804-16-8Relevant articles and documents
Stereoselective Synthesis of Cyclohepta[b]indoles by Visible-Light-Induced [2+2]-Cycloaddition/retro-Mannich-type Reactions
Mu, Xin-Peng,Li, Yuan-He,Zheng, Nan,Long, Jian-Yu,Chen, Si-Jia,Liu, Bing-Yan,Zhao, Chun-Bo,Yang, Zhen
, p. 11211 - 11216 (2021)
A novel method for the concise synthesis of cyclohepta[b]indoles in high yields was developed. The method involves a visible-light-induced, photocatalyzed [2+2]-cycloaddition/ retro-Mannich-type reaction of enaminones. Experimental and computational studies suggested that the reaction is a photoredox process initiated by single-electron oxidation of an enaminone moiety, which undergoes subsequent cyclobutane formation and rapidly fragmentation in a radical-cation state to form cyclohepta[b]indoles.
Metal-Free Dearomatization: Direct Access to Spiroindol(en)ines in Batch and Continuous-Flow
Ranjan, Prabhat,Ojeda, Gerardo M.,Sharma, Upendra K.,Van der Eycken, Erik V.
supporting information, p. 2442 - 2446 (2019/01/29)
A metal-free, phosphine-catalyzed intramolecular “umpolung Michael addition” on alkynes to form spiroindol(en)ines is reported. This nucleophilic catalysis enables the formation of a wide scope of five- and six-membered spiroindol(en)ines in moderate to excellent yields in batch as well as under continuous-flow conditions. Triphenylphosphine-catalyzed nucleophilic activation of alkynes allows the exclusive formation of exo-product under mild reaction conditions.
Directed evolution of RebH for catalyst-controlled halogenation of indole C-H bonds
Andorfer, Mary C.,Park, Hyun June,Vergara-Coll, Jaylie,Lewis, Jared C.
, p. 3720 - 3729 (2016/06/09)
RebH variants capable of chlorinating substituted indoles ortho-, meta-, and para-to the indole nitrogen were evolved by directly screening for altered selectivity on deuterium-substituted probe substrates using mass spectrometry. This systematic approach allowed for rapid accumulation of beneficial mutations using simple adaptive walks and should prove generally useful for altering and optimizing the selectivity of C-H functionalization catalysts. Analysis of the beneficial mutations showed that structure-guided selection of active site residues for targeted mutagenesis can be complicated either by activity/selectivity tradeoffs that reduce the possibility of detecting such mutations or by epistatic effects that actually eliminate the benefits of a mutation in certain contexts. As a corollary to this finding, the precise manner in which the beneficial mutations identified led to the observed changes in RebH selectivity is not clear. Docking simulations suggest that tryptamine binds to these variants as tryptophan does to native halogenases, but structural studies will be required to confirm these models and shed light on how particular mutations impact tryptamine binding. Similar directed evolution efforts on other enzymes or artificial metalloenzymes could enable a wide range of C-H functionalization reactions.