Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Homopropargyl Amines Bearing All-Carbon Quaternary Stereocenters via Chirality Transfer of Hindered Allenylcopper Species DOI

Jing He,

Wan Seok Yoon, Jaesook Yun

и другие.

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 578 - 584

Опубликована: Дек. 23, 2024

The construction of congested acyclic stereocenters with high stereoselectivity is a significant challenge in synthetic chemistry. Herein, we report an efficient method for diastereo- and enantioselective C–C coupling 1,3-disubstituted enynes imines the asymmetric vicinal stereogenic centers, including all-carbon quaternary center. This was accomplished by chirality transfer from axial-to-central fully substituted axially chiral allenylcopper intermediates formed situ branched concomitant diastereoselective formation additional stereocenter imine addition enabled C1-symmetric N-heterocyclic carbene (NHC) copper catalyst. DFT calculations provided enhanced understanding silyl effect nucleophiles on reactivity origin stereoselectivity. Synthetic versatility resulting products bearing densely functionalized groups could amplify significance current method.

Язык: Английский

Ni/Cu Dual‐Catalyzed Propargylation for the Stereodivergent Synthesis of Methohexital DOI Creative Commons
Xihao Chang, Jiayin Zhang, Xiang Cheng

и другие.

Advanced Science, Год журнала: 2024, Номер unknown

Опубликована: Июль 25, 2024

The development of efficient methodologies for the controlled manufacture specific stereoisomers bearing quaternary stereocenters has prompted advances in a variety scientific disciplines including pharmaceutical chemistry, materials science, and chemical biology. However, complete control absolute relative stereochemical configurations alkyne derivatives remains an unmet synthetic challenge. Herein, Ni/Cu dual-catalyzed asymmetric propargylic substitution reaction is presented to produce propargylated products with all-carbon high yields significant diastereo- enantioselectivities (up >20:1 dr, >99% ee). synthesis all variants methohexital, widely used sedative-hypnotic drug, exemplifies efficacy stereodivergent propargylation.

Язык: Английский

Процитировано

2
Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Homopropargyl Amines Bearing All-Carbon Quaternary Stereocenters via Chirality Transfer of Hindered Allenylcopper Species DOI

Jing He,

Wan Seok Yoon, Jaesook Yun

и другие.

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 578 - 584

Опубликована: Дек. 23, 2024

The construction of congested acyclic stereocenters with high stereoselectivity is a significant challenge in synthetic chemistry. Herein, we report an efficient method for diastereo- and enantioselective C–C coupling 1,3-disubstituted enynes imines the asymmetric vicinal stereogenic centers, including all-carbon quaternary center. This was accomplished by chirality transfer from axial-to-central fully substituted axially chiral allenylcopper intermediates formed situ branched concomitant diastereoselective formation additional stereocenter imine addition enabled C1-symmetric N-heterocyclic carbene (NHC) copper catalyst. DFT calculations provided enhanced understanding silyl effect nucleophiles on reactivity origin stereoselectivity. Synthetic versatility resulting products bearing densely functionalized groups could amplify significance current method.

Язык: Английский

Процитировано

1