Spiro‐Bicyclic Bisborane Catalysts for Metal‐Free Chemoselective and Enantioselective Hydrogenation of Quinolines

Li, Xiang; Tian, Jun‐Jie; Liu, Ning; Tu, Xian-Shuang; Zeng, Ning-Ning; Wang, Xiao‐Chen

doi:10.1002/ange.201900907

Cited by 24 publications

(5 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…reinvented the catalyst and achieved up to 99% ee in the asymmetric hydrogenation of imines and enamines using a N/B FLP catalyst 32 with a binaphthyl backbone. [ 58 ] Very recently, the catalyst 33 based on a spiro‐bicyclic backbone, enabled hydrogenation of quinolines with excellent yields and ee s. [ 59 ] Piers’ borane and chiral tert ‐butylsulfinamide are chosen as the FLP 34 , furnishing the transfer hydrogenation of imines in 78%—99% yields with up to 95% ee . [ 60 ]…”

Section: Overviews In Catalysismentioning

confidence: 99%

Frustrated Lewis Pairs: Discovery and Overviews in Catalysis

Zhang

2020

Chin. J. Chem.

View full text Add to dashboard Cite

Frustrated Lewis Pairs (FLPs) are derived from simple combinations of Lewis acids (electron acceptors) and Lewis bases (electron donors), in which steric demands prevent from forming classical Lewis acid-base adducts. Since 2006, FLP chemistry has emerged as a novel strategy for the design and application of main-group chemistry and development of new metal-free catalytic processes. This strategy has been applied to stoichiometric reactivity and then extended to catalysis. In this review, we briefly summarize the representative discoveries and developments of FLP chemistry in the field of catalysis, including hydrogenation, hydrosilylation, reduction of CO2, transformations of alkynes to organic derivatives, C-H bond borylation and polymerization. Nan Li (left) was born in Henan, China, in 1988. She received her BS degree from Xinyang University in 2012. She obtained her PhD degree in 2017, supervised by Professor Bing-Tao Guan at Nankai University. Following her graduate research, she moved to the college of chemistry at Peking University as a Postdoctoral Fellow in the laboratory of Professor Zhenfeng Xi and Professor Wen-Xiong Zhang (2017-2019). Wen-Xiong Zhang (right) received his B.Sc. from Hunan Normal University in 1996, his MSc from Guangxi Normal University in 1999, and his PhD from Nankai University with professor Li-Cheng Song in 2003. He carried out postdoctoral research at Peking University with Prof. Zhenfeng Xi and at Riken in Japan with Prof. Zhaomin Hou. In 2007, he joined College of Chemistry at Peking University as an Associate Professor, where he is now a Professor. His research interests include design, synthesis and small molecule activation of rare-earth-metal heterocycles, metal-catalyzed C-N bond activation, and carbodiimide-based organic synthesis to construct N-containing heterocycles.

show abstract

Section: Overviews In Catalysismentioning

confidence: 99%

Frustrated Lewis Pairs: Discovery and Overviews in Catalysis

Zhang

2020

Chin. J. Chem.

View full text Add to dashboard Cite

show abstract

“…1a). Catalytic regioselective hydrogenation and transfer hydrogenation of N-heteroarenes have attracted intense interest [16][17][18][19][20][21][22][23][24][25] , and could provide the most straightforward protocol with which to harvest the desired DHQs. However, catalytic transformation of quinolines to DHQs is extremely challenging.…”

mentioning

confidence: 99%

Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis

et al. 2020

View full text Add to dashboard Cite

Catalytic hydrogenation or transfer hydrogenation of quinolines was thought to be a direct strategy to access dihydroquinolines. However, the challenge is to control the chemoselectivity and regioselectivity. Here we report an efficient partial transfer hydrogenation system operated by a cobalt-amido cooperative catalyst, which converts quinolines to 1,2-dihydroquinolines by the reaction with H 3 N•BH 3 at room temperature. This methodology enables the large scale synthesis of many 1,2-dihydroquinolines with a broad range of functional groups. Mechanistic studies demonstrate that the reduction of quinoline is controlled precisely by cobalt-amido cooperation to operate dihydrogen transfer from H 3 N•BH 3 to the N=C bond of the substrates.

show abstract

“…To get a better stereocontrol over less bulky substrates like 2‐methylquinoline, internal bicyclic [3.3.0] dienes 39 were then replaced by a spiro‐bicyclic structure, in which the presence of two perpendicular rings, Ar and BAr F 2 substituents attached to the rings increase the steric hindrance . The synthesis of chiral spiro dienes 48 started from ethyl 2‐oxocyclopentanecarboxylate 41 .…”

Section: Chiral Boranes Synthesized Via In Situ Hydroborationmentioning

confidence: 99%

Asymmetric Catalysis with Chiral Frustrated Lewis Pairs

Meng

Feng

2020

Chin. J. Chem.

View full text Add to dashboard Cite

The chemistry of frustrated Lewis pairs (FLPs) provides the most important approach for the metal-free hydrogenation and hydrosilylations. Great progress has been achieved in this area for the past decade. Some promising results have also been obtained. This perspective article mainly focuses on the recent advances for the synthesis of chiral Lewis acidic boranes in category of three protocols, 1) hydroboration of chiral internal alkenes with Piers' borane HB(C6F5)2; 2) in situ hydroboration of chiral alkenes or alkynes without any purification; 3) and substitution reaction of (C6F5)nBCl3-n with chiral organometallic reagents, as well as their applications in the metal-free asymmetric hydrogenations and hydrosilylations.

show abstract

Spiro‐Bicyclic Bisborane Catalysts for Metal‐Free Chemoselective and Enantioselective Hydrogenation of Quinolines

Cited by 24 publications

References 58 publications

Frustrated Lewis Pairs: Discovery and Overviews in Catalysis

Frustrated Lewis Pairs: Discovery and Overviews in Catalysis

Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis

Asymmetric Catalysis with Chiral Frustrated Lewis Pairs

Contact Info

Product

Resources

About