Access to Enantioenriched Benzylic 1,1-Silylboronate Esters by Palladium-Catalyzed Enantiotopic-Group Selective Suzuki-Miyaura Coupling of (Diborylmethyl)silanes with Aryl Iodide

Junghoon Kim ,  Seung Hwan Cho*

 

본 연구에서는 이붕소화메틸 실리콘 화합물을 이용하여 팔라듐 촉매와 키랄성 인 리간드를 이용하여 비대칭 1,1-실릴붕소화합물을 합성하는데에 성공하였다. 이 반응은 다양한 기질에 대하여 매우 높은 입체선택성과 수율을 나타내었고, 합성된 키랄성 1,1-실릴붕소화합물은 입체특이적 반응을 통해 다양한 종류의 키랄성 물질을 합성하는데에 응용이 가능함을 보여주었다.  본 연구결과는 2018년 12월 7 일 ACS Catalysis에 게재되었다.

 

 

This work describes the palladium-catalyzed enantiotopic-group selective Suzuki–Miyaura cross-coupling of (diborylmethyl)silanes with aryl iodides. The combination of a Pd(TFA)₂ and rev-Josiphos-type ligand bearing a 3,5-bis(trifluoromethyl)phenyl as benzylic phosphine substituent in the presence of NaI as an additive and NaOMe as a base promote the reaction to high efficiency and excellent enantioselectivity. This method provides a convenient approach for synthesizing chiral benzylic 1,1-silylboronate esters from readily accessible reagents. Synthetic applications including stereospecific C–O, C–N, and C–C bond forming reactions of boron group are also demonstrated.

 


https://pubs.acs.org/doi/10.1021/acscatal.8b03979