Rhodium‐Catalyzed Asymmetric Synthesis of Spirosilabifluorene Derivatives

Ir-Catalyzed Enantioselective, Intramolecular Silylation of Methyl C–H Bonds

“…9 In 2013, Takai, Kuninubu, and co-workers published the first enantioselective silylation of aromatic C–H bonds. 10 The reaction was catalyzed by a rhodium complex ligated by a chiral diphosphine (Scheme 1a, left), forming chiral spirosila-bifluorenes in up to 90.5:9.5 er. In 2015, Shibata, He, and Takai independently reported enantioselective silylations of aromatic C–H bonds that form chiral ferrocenes (Scheme 1a, middle) catalyzed by Rh complexes of chiral bisphosphine or diene ligands.…”

The Development of Novel C-H Bond Transformations and Their Application to the Synthesis of Organic Functional Molecules

“…28 31 π Conjugated molecules containing heteroatom(s), such as sila uorene derivatives, have important uses as organic functional materials such as uorophores, and in solar cell devices. We have reported the synthesis of sila uorene derivatives 28,29 and phospha uorene oxides 30 by intramolecular C H/heteroatom H coupling reactions. Another strategy for the synthesis of heteroatom containing π conjugated molecules is C H/C H coupling reaction of heteroatom bridged biaryl compounds (Scheme 19).…”

Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et2SiH2

“…Silafluorenes 8 and 9 were separated by column chromatography. Keywords: CÀC activation · density functional calculations · nickel · SiÀ H activation · silanes ion formed in the reaction of HSi-functionalized 2-silylbiphenyl derivatives 2A C H T U N G T R E N N U N G (R 2 HSi) and the trityl cation [18] or by Rh-catalyzed H 2 elimination from 2A C H T U N G T R E N N U N G (R 2 HSi) and subsequent CÀC coupling; [19][20][21] iii) by Ir-catalyzed [2+2+2] cycloaddition of silicon-bridged 1,6-diynes with alkynes; [22] and iv) by metathesis reactions of 2,2'-dimetalated biphenyls and R 2 SiX 2 [8,[23][24][25][26] or triorganyl silanes R 3 SiX. [27][28][29] Furthermore, a Pd-catalyzed reaction starting from 2,2-dihalogenated biphenyls and Et 2 SiH 2 has also been reported.…”