Chiral Dienes: From Ligands to FLP Catalysts

Abstract

Comprehensive SummaryOlefins are very easily accessible compounds which are both popular substrates in synthetic chemistry and good ligands in the organometallic complexes. This dual character makes olefins a rich source of chiral ligands and catalysts for asymmetric catalysis. Herein, we will briefly summarize our studies on the development of chiral diene ligands for transition‐metal catalyzed asymmetric reactions and chiral FLP catalysts for asymmetric metal‐free hydrogenations and hydrosilylations. Several acyclic chiral diene ligands as well as P/olefin and S/olefin hybrid ligands were developed for Rh or Pd‐catalyzed asymmetric reactions. With these ligands in hand, we further put forward a novel strategy for acquiring chiral FLP catalysts via the in situ hydroboration of chiral dienes with Piers’ borane. These catalysts proved to be highly effective for asymmetric metal‐free hydrogenations and hydrosilylations of imines, silyl enol ethers, ketones, and aromatic N‐heterocycles. What is the most favorite and original chemistry developed in your research group?The development of acyclic dienes both as chiral ligands and as precursors of chiral FLP catalysts.How do you get into this specific field? Could you please share some experiences with our readers?When I started my independent research in 2008, chiral olefins belong to one novel ligand type. We got into the field with the thought of the simpler the better. This experience further led us to step into FLP catalysis.What is the most important personality for scientific research?Courage and persistence of doing something unique.What are your hobbies?Walking and playing cards.How do you keep balance between research and family?Life is not only research, but also family. You believe it, the balance is there.What is your favorite journal(s)?My favorite journal is Organic Letters, in which authors can publish their work rapidly and readers can browse the progress of organic chemistry comprehensively.

Chiral Diene Ligands in Asymmetric Catalysis

“…This review does not deal with achiral diene ligands or chiral monoolefin ligands, such as P−olefin, N− olefin, and S−olefin hybrid ligands. The use of chiral dienes as starting compounds for the synthesis of chiral organocatalysts, typically chiral frustrated Lewis pairs, 26 is an interesting research field, but it is beyond the scope of this review.…”

Asymmetric catalysis by chiral FLPs: A computational mini‐review

“…Rigidity in the catalyst is also an important aspect that determines the enantioselectivity in the product formation. In this regard, the binaphthyl derivatives are the ideal choice, and accordingly, chiral LAs 5 , 6 , and 7 were synthesized 71–73 . Du and co‐workers employed the LA 5 and increased the ee up to 89% 74 .…”

“…In this regard, the binaphthyl derivatives are the ideal choice, and accordingly, chiral LAs 5, 6, and 7 were synthesized. [71][72][73] Du and co-workers employed the LA 5 and increased the ee up to 89%. 74 In situ generation of the catalyst was performed by hydroboration reaction of chiral binaphthyl anchored alkene with HB(C 6 F 5 ) 2 .…”