銅触媒による有機およびシリルボロン酸エステルを用いた不斉アリル位置換反応

京都大学0048新制・課程博士博士(理学)甲第18093号理博第3971号新制||理||1572(附属図書館)30951京都大学大学院理学研究科化学専攻(主査)教授 大須賀 篤弘, 教授 丸岡 啓二, 教授 時任 宣博学位規則第4条第1項該当Doctor of ScienceKyoto UniversityDGA

Enantioselective Synthesis of α‑Tri- and α‑Tetrasubstituted Allylsilanes by Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Silylboronates

A copper/<i>N</i>-heterocyclic carbene-catalyzed asymmetric allylic substitution of allyl phosphates with a silylboronate has been developed to give highly enantioenriched allylsilanes. High regioselectivity has been achieved by employing NaOH as the base, and this catalyst system is effective for both γ-mono- and disubstituted allyl phosphates

Synthesis of 3‑Mono-Substituted Binaphthyl-Based Secondary Amine Catalysts via Monobromination of an Axially Chiral Dicarboxylic Acid Derivative

A facile synthetic route to a 3-bromo binaphthyl-based secondary amine through the monobromination of an axially chiral dicarboxylic acid derivative has been developed. The combination of this new procedure with coupling reactions established an efficient synthetic approach to a series of binaphthyl-based secondary amine catalysts containing various functional groups in an efficient way

Synthesis of Quaternary Carbon Stereocenters by Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Arylboronates

A copper-catalyzed asymmetric allylic substitution of γ,γ-disubstituted allyl phosphates with arylboronates has been developed for the construction of quaternary stereocenters. High regio- and enantioselectivities have been achieved by employing a hydroxy-bearing chiral <i>N</i>-heterocyclic carbene ligand, and both <i>E</i> and <i>Z</i> substrates provide the same enantiomer as the major product. The mechanistic aspect of this catalysis has also been investigated to find that a 1:1 copper/ligand complex is most likely responsible for the present asymmetric catalysis, and the reaction proceeds with almost perfect 1,3-<i>anti</i> stereochemistry with respect to the allylic electrophile

Synthesis of Quaternary Carbon Stereocenters by Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Arylboronates

A copper-catalyzed asymmetric allylic substitution of γ,γ-disubstituted allyl phosphates with arylboronates has been developed for the construction of quaternary stereocenters. High regio- and enantioselectivities have been achieved by employing a hydroxy-bearing chiral <i>N</i>-heterocyclic carbene ligand, and both <i>E</i> and <i>Z</i> substrates provide the same enantiomer as the major product. The mechanistic aspect of this catalysis has also been investigated to find that a 1:1 copper/ligand complex is most likely responsible for the present asymmetric catalysis, and the reaction proceeds with almost perfect 1,3-<i>anti</i> stereochemistry with respect to the allylic electrophile