Recent Advances in Ligand-Controlled Regio- or Stereodivergent Transition-Metal-Catalyzed Hydroelementation (H[E]) (E = H, B, Si, Ge) of C–C Unsaturated Systems DOI
Sehoon Park

Synthesis, Journal Year: 2024, Volume and Issue: 56(20), P. 3083 - 3107

Published: May 31, 2024

Abstract Reductive functionalization of C–C unsaturated systems, including alkenes and alkynes, with a range hydroelements (H[E]) is one the most fundamental highly practical methods for synthesis functionalized hydrocarbons. Since resultant hydrocarbon products have strong applicability as synthetic intermediates, numerous homogeneous organo(metallic) catalysts been intensively utilized to date reductive reactions. In particular, well-defined transition-metal-based capable controlling regio- or stereoselectivity product by harnessing addition H[E] (E = H, B, Si, Ge) into Cα–Cβ bonds drawn special attention. this review, we describe recent examples transition-metal catalytic systems (M Fe, Co, Rh, Pd, Ni) stereodivergent hydroelementation reactions (conjugated) alkenes, allenes give pair isomeric in high selectivities from same starting compounds simply variation ligand. Mechanistic aspects ligand-controlled selectivity divergence are discussed detail on basis experimental observations and/or computational insights. 1 Introduction 2 Hydroelementation Alkenes Alkynes 3 Conjugated Dienes Diynes 4 Allenes 5 Summary Outlook

Language: Английский

Trifluoromethyl Group (CF3) Induced Regioselective Larock Indole Synthesis from Unsymmetric β-CF3-1,3-enynes DOI

Yan‐Hua Qiu,

Peng-Xiang Ma,

Wen‐Hao Shao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

The indole skeleton exists widely in natural products, pharmaceuticals, and materials. We disclose here a trifluoromethyl group induced regioselective Larock synthetic method from unsymmetric 2-CF3-1,3-enynes. presence of is determinable for the regioselectivity. Once CF3 was replaced with methyl or phenyl group, ratio 1:1 to 1:1.4 isomers were obtained. This strategy features good regioselectivity, broad substrate scope, high functional tolerance. protocol reported offers an alternative solution rare 3,4-functionalization products further transformed show distinctive reactivity hydroboration–oxidation hydro-bromination.

Language: Английский

Citations

0
Visible-Light-Induced trans-Hydroboration of Diaryl Alkynes Utilizing Excited State of Borate Complexes DOI

Takahiro Komaki,

Yu Sato,

Masanobu Uchiyama

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(11), P. 2180 - 2185

Published: March 11, 2024

We have developed visible-light-induced trans-hydroboration of diaryl alkynes via direct photoexcitation in-situ-generated diboron complexes, affording previously elusive (E)-1,2-diaryl-vinylboronates with high stereoselectivity. Experimental, spectroscopic, and theoretical mechanistic studies revealed that the triplet-state borate complex facilitates B–B bond cleavage desired C–B formation. This methodology does not require any catalyst is operationally simple. The highly borylated 1,2-diaryl alkenes [1-(2-borylphenyl)vinyl)boronates] are shown to be useful as building blocks.

Language: Английский

Citations

3
Redox‐Neutral Nickel‐Catalyzed Selective Hydroalkynylation of Internal Alkyne and Its Application in Anticancer Agent Discovery† DOI
Weiming Chen, Teng Liu, Shuqing Li

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 4, 2024

Comprehensive Summary Herein, an unprecedented nickel‐catalyzed regioselective hydroalkynylation of unsymmetrical internal alkynes was realized with steric hindered resistance selectivity via the cyano‐directing group strategy. Significantly, resulting 1,3‐enyne products could be effectively employed in synthesis novel nitrogen‐containing tricyclics compounds, that provided potential candidate compound 8a (IC 50 = 2.6—6.1 μmol/L) for anti‐tumor cell proliferation activity. Therefore, this work not only improves transition‐metal‐ catalyzed strategy alkynes, but also exhibits versatility 1,3‐enynes construction complex bioactive chemical space.

Language: Английский

Citations

1
Recent Advances in Ligand-Controlled Regio- or Stereodivergent Transition-Metal-Catalyzed Hydroelementation (H[E]) (E = H, B, Si, Ge) of C–C Unsaturated Systems DOI
Sehoon Park

Synthesis, Journal Year: 2024, Volume and Issue: 56(20), P. 3083 - 3107

Published: May 31, 2024

Abstract Reductive functionalization of C–C unsaturated systems, including alkenes and alkynes, with a range hydroelements (H[E]) is one the most fundamental highly practical methods for synthesis functionalized hydrocarbons. Since resultant hydrocarbon products have strong applicability as synthetic intermediates, numerous homogeneous organo(metallic) catalysts been intensively utilized to date reductive reactions. In particular, well-defined transition-metal-based capable controlling regio- or stereoselectivity product by harnessing addition H[E] (E = H, B, Si, Ge) into Cα–Cβ bonds drawn special attention. this review, we describe recent examples transition-metal catalytic systems (M Fe, Co, Rh, Pd, Ni) stereodivergent hydroelementation reactions (conjugated) alkenes, allenes give pair isomeric in high selectivities from same starting compounds simply variation ligand. Mechanistic aspects ligand-controlled selectivity divergence are discussed detail on basis experimental observations and/or computational insights. 1 Introduction 2 Hydroelementation Alkenes Alkynes 3 Conjugated Dienes Diynes 4 Allenes 5 Summary Outlook

Language: Английский

Citations

0