銥催化下C-H鍵反應(yīng)

1、Unactivated Methyl C（spsp3 3)-)-H Bonds High Stereoselective Intramolecular Silylation ReactionBo Su; John F. Hartwig; J. Am. Chem. Soc. 2017, 139, 12137-12140.Speaker:Wang Wan LinDate： 10.15.2017Introduction Education & Position1986. B.A.Princeton Univ 1990. Ph.D.Chemistry, Univ.of California,Berke

2、ley1992. American Cancer Society Postdoctoral Associate, Massachusetts Institute of Technology2011-present. Univ. of California, Berkeley, and Senior Faculty Scientist, Lawrence Berkeley National LaboratoryHartwig, John F. ProfessorIntroduction Awards & Honors2010. GlaxoSmithKline Scholars Award 200

3、9. National Institutes of Health MERIT Award 2009. Mitsui Chemicals Catalysis Science Award, Japan2009. Joseph Chatt Award of the Royal Society of Chemistry2008. Mukaiyama Award from the Society of Synthetic Organic Chemistry, Japan 2008. International Catalysis Award, International Association of C

4、atalysis Societies2008 . Paul N. Rylander Award2007. Young Investigator Award2007. Raymond and Beverly Sackler Prize in the Physical Sciences2006. ACS Award in Organometallic.Chemistry 2004. Thieme-IUPAC Award2003. Leo Hendrik Baekeland Award 1998. A.C. Cope Scholar AwardResearch areas Focuses on th

5、e discovery and understanding of new reactions of organic compounds catalyzed by transition metal complexes.BackgroundRepresentative biologically active silicon-containing molecules. In 2013, Takai, Kuninubu, and co-workers published the first enantioselective silylation of aromatic C（sp2)H bonds. I

6、n 2015, Shibata, He, and Takai, He wei independently reported enantioselective silylations of aromatic C（sp2)H bonds that form chiral ferrocenes catalyzed by Rh complexes of chiral bisphosphine or diene ligands. Author group reported Rh-catalyzed enantioselective silylations of aromatic C(sp2)H bond

7、s in diarylmethanols and silylations of cyclopropyl C(sp3)H bondsSo far, only the Kazuhiko Takai group reported asymmetric silylation of non-activated C (sp3) -H bondsIn 2013, Takai, Kuninubu, and co-workers published the first enantioselective silylation of aromatic CH bonds.Angew. Chem. Int. Ed. 2

8、013, 52, 15201522He wei reported enantioselective silylations of aromatic C(sp2)H bonds that form chiral ferrocenes catalyzed by Rh complexes of chiral bisphosphine or diene ligands.Angew. Chem. Int. Ed. 2015, 54, 69186921 ligandsAuthor group reported Rh-catalyzed enantioselective silylations of aro

9、matic C(sp2)H bonds in diarylmethanols and silylations of cyclopropyl C(sp3)H bondsJ. Am. Chem. Soc. 2015, 137, 67426745Angew. Chem. Int. Ed. 2016, 55, 87238727Kazuhiko Takai group reported asymmetric silylation of non-activated C (sp3) -H bonds Murai, M.; Takeshima, H.; Morita, H.; Kuninobu,Y.; Tak

10、ai, K. J. Org. Chem. 2015, 80, 5407.Angew. Chem. Int. Ed. 2016, 55, 16 Iridium-Catalyzed Silylation of Aromatic C-H Bonds Ir(COD)OMe 2 and chiral dinitrogen ligands Transformations of the Enantioenriched Dihydrobenzosilolesa (a) Ir(cod)OMe2 (0.50 mol %), L 4 , (1.1 mol%), nbe, Et 2 O, 50 C; (b) t-Bu

11、OOH, t-BuOK, TBAF; (c) NIS, AgF,MeCN; (d) NBS, AgF, MeCN; (e) NCS, AgF, MeCN; (f) t-BuOOH,KH, TBAF; (g) HCl, THF/H 2 O; (h) DEAD, PPh 3 , THF.Sequential Silylations of CH BondsDiastereoselective Silylation of the C(sp3)H Bond of Dehydroabietic Acid Derivativea Reaction conditions: (a) Mg, THF, Me2Si

12、HCl; (b) Ir(cod)OMe2/L4 , nbe, Et2O.J. Am. Chem. Soc. 2014, 136, 65866589 Angew. Chem. Int. Ed. 2016, 55, 87238727 kH/ kD 27 Summary1. The authors use the Ir (COD) OMe / N, N ligand system for the first time to achieve the iridium-catalyzed enantioselective unactivated C (sp3) -H bond silylation rea

13、ction.2. The reaction substrate is wide, the yield is high, the enantioselectivity is good, and the C-Si bond is successfully converted into CO, C-Cl, C-Br, CI and so on, which greatly improves the use value of the reaction , The author also used the reaction to achieve the synthesis of some living active molecules.3. The authors determined the absolute configuration of the prod