Enantioselective Hydrophosphination of Terminal Alkenyl Aza‐Heteroarenes DOI Creative Commons
Esther G. Sinnema, Tizian‐Frank Ramspoth, Reinder H. Bouma

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(7)

Published: Dec. 22, 2023

Abstract This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful diverse range alkenyl‐heteroarenes with high enantioselectivity. presented protocol addresses inherently low reactivity and commonly encountered suboptimal enantioselectivities these challenging substrates. As an important application we show that this method facilitates synthesis non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using single catalytic system.

Language: Английский

Unlocking the potential of metal ligand cooperation for enantioselective transformations DOI Creative Commons
Tizian‐Frank Ramspoth, Johanan Kootstra, Syuzanna R. Harutyunyan

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3216 - 3223

Published: Jan. 1, 2024

Metal–ligand cooperation, (MLC) is a versatile catalysis concept. Herein, we discuss the historical context, mechanisms, and applications, suggesting exploring MLC for enantioselective transformations beyond (de)hydrogenative processes.

Language: Английский

Citations

11
Manganese(I)-Catalyzed Enantioselective Alkylation To Access P-Stereogenic Phosphines DOI Creative Commons
Baonian Wan, Marta Castiñeira Reis, Tizian‐Frank Ramspoth

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

This work introduces a novel Mn(I)-catalyzed enantioselective alkylation methodology that efficiently produces wide array of P-chiral phosphines with outstanding yields and enantioselectivities. Notably, the exceptional reactivity Mn(I) complexes in these reactions is demonstrated by their effective catalysis both typically reactive alkyl iodides bromides, as well less chlorides. approach broadens accessibility to various simplifies synthesis chiral tridentate pincer concise 1–2 step process, contrary conventional, labor-intensive multistep procedures. Importantly, development significantly expands applicability earth-abundant Mn(I)-based beyond recently established roles catalytic hydrogenative conjugate addition reactions, emphasizing potential viable alternative noble metal chemistry and, some cases, even surpassing performance.

Language: Английский

Citations

0
Enantioselective Hydrophosphination of Terminal Alkenyl Aza‐Heteroarenes DOI Creative Commons
Esther G. Sinnema, Tizian‐Frank Ramspoth, Reinder H. Bouma

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 22, 2023

Abstract This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful diverse range alkenyl‐heteroarenes with high enantioselectivity. presented protocol addresses inherently low reactivity and commonly encountered suboptimal enantioselectivities these challenging substrates. As an important application we show that this method facilitates synthesis non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using single catalytic system.

Language: Английский

Citations

8
Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes DOI Creative Commons

Narendra Kumar Vaishanv,

Nadim Eghbarieh, Rahul A. Jagtap

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 9, 2024

Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.

Language: Английский

Citations

1
Manganese-Catalyzed Z-Selective Allylation of Indoles with Allenyl Derivatives DOI

Doppalapudi Vineet Kumar,

Basker Sundararaju

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(14), P. 10087 - 10092

Published: July 10, 2024

Herein, we report a manganese-catalyzed

Language: Английский

Citations

1
Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes DOI Creative Commons

Narendra Kumar Vaishanv,

Nadim Eghbarieh, Rahul A. Jagtap

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 9, 2024

Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.

Language: Английский

Citations

0
Iridium-Catalyzed Ligand-Controlled Semi-Reduction of Alkynes Employing H2O as the Hydrogen Donor and Its Application DOI
Wei Zhao,

Siyi Zhou,

Yi Zhang

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(12), P. 1405 - 1410

Published: Nov. 2, 2023

Abstract An iridium-catalyzed ligand-controlled semi-reduction of alkynes employing H2O as the hydrogen donor, together with its application, is reported. The use di-tert-butylphosphinous chloride crucial for stereoselectivity toward Z-olefins, whereas 2-(diphenylphosphino)benzaldehyde E-olefins. More than 35 alkenes were obtained in good yields and high stereoselectivities. utility current method practical applications was investigated by studying drug effects (E)-1,3-dimethoxy-5-styrylbenzene on nerve growth a zebrafish model.

Language: Английский

Citations

0
Enantioselective Hydrophosphination of Terminal Alkenyl Aza‐Heteroarenes DOI Creative Commons
Esther G. Sinnema, Tizian‐Frank Ramspoth, Reinder H. Bouma

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(7)

Published: Dec. 22, 2023

Abstract This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful diverse range alkenyl‐heteroarenes with high enantioselectivity. presented protocol addresses inherently low reactivity and commonly encountered suboptimal enantioselectivities these challenging substrates. As an important application we show that this method facilitates synthesis non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using single catalytic system.

Language: Английский

Citations

0