Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

Zhang, Fenghua; Guo, Xiaochong; Zeng, Xianrong; Wang, Zhaobin

doi:10.1038/s41467-022-32614-4

Cited by 57 publications

(22 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Wang et al, in 2022, reported an asymmetric 1,4-difunctionalization of 1,3-enynes using dual photoredox and Cr catalysts. The reaction of 1,3-enynes with aldehydes and DHP esters in the presence of CrCl 2 , 4CzIPN and chiral ligand under the radiation of blue LEDs afforded chiral allenols 41 in moderate to good yields with high enantioselectivities ( Scheme 40 ) [ 75 ]. The reaction mechanism suggests that isopropyl radical generated from DHP ester assisted adds to 1,3-enyne to provide propargyl radical M-87 followed by trapping with Cr II L to form the propargyl chromium M-88 and then chiral intermediate M-89 after nucleophilic addition to benzaldehyde.…”

Section: 14-difunctionalization Reactionsmentioning

confidence: 99%

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Zhang

2023

Molecules

View full text Add to dashboard Cite

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction of functional groups. In radical difunctionalization reactions, the radicals in the first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, and ring opening. The resulting radical intermediates can undertake the following paths for the second functionalization: (1) couple with other radical groups, (2) oxidize to cations and then react with nucleophiles, (3) reduce to anions and then react with electrophiles, (4) couple with metal-complexes. The rearrangements of radicals provide the opportunity for the synthesis of 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalization products. Multiple ways to initiate the radical reaction coupling with intermediate radical rearrangements make the radical reactions good for difunctionalization at the remote positions. These reactions offer the advantages of synthetic efficiency, operation simplicity, and product diversity.

show abstract

Section: 14-difunctionalization Reactionsmentioning

confidence: 99%

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Zhang

2023

Molecules

View full text Add to dashboard Cite

show abstract

“…Very recently, Wang's group developed the cooperative photoredox and chromium catalyzed asymmetric 1,4-functionalization of 1,3-enynes, leading to chiral allenols 83 possessing axial and central chiralities in good results (Scheme 19). [34] A putative mechanism is outlined in Scheme 19. It was reasoned that the excited photocatalyst was quenched by the DHP ester 81 a to generate the reduced photocatalyst, the isopropyl radical 32 a and pyridinium 84.…”

Section: Metallaphotoredox Catalyzed Reactions Involving Allenyl Radi...mentioning

confidence: 99%

Allenyl Radicals in Organic Synthesis: Challenges and Recent Advances

Zhang

2022

Eur J Org Chem

View full text Add to dashboard Cite

Allenyl radicals are rarely employed as intermediates for the synthesis of allenes probably owe to the lack of convenient methods for their generation and the high reactivity of short‐lived allenyl radicals. However, strategies take advantage of allenyl radicals are considered as a significant complement to reactions which couldn't proceed via an allenyl ionic pathway. As a result, several important methods have been developed in the past decades. Herein, this review is aimed to summarize the recent advance in reactions involving allenyl radicals by highlighting some outstanding challenges and confirming potential areas of improvement, which would offer an inspiration for future studies

show abstract

“…In 2022, the group of Xiao [9] , Li [10] , and Shi [11] independently realized Co/PC dual-catalyzed or Nicatalyzed reductive coupling of aryl halides with aldehydes. With the significant achievement, the simultaneous construction of multiple chiral elements [12] still remains elusive, especially for biaryl axially chiral secondary alcohol.…”

Section: Introductionmentioning

confidence: 99%

Visible light-mediated cobalt and photoredox dual-catalyzed asymmetric reductive coupling of biaryl dialdehydes and aryl iodides

Liang

Sun

et al. 2023

Preprint

View full text Add to dashboard Cite

Secondary alcohols bearing both axial and central chirality comprise attractive biological activity, and also exhibit excellent chiral induction in asymmetric reactions. However, only very limited asymmetric catalytic approaches were developed for their catalytic synthesis. We herein describe visible light-mediated cobalt-catalyzed asymmetric reductive Grignard-type addition of axially prochiral biaryl dialdehydes with aryl iodides, leading to the direct construction of axially chiral secondary alcohols bearing aldehyde groups. Preliminary mechanistic studies indicate efficient kinetic recognition of diastereomers might occur to improve the diastereoselectivity, which might open a new avenue for the challenging cascade construction of multiple chiral elements. This protocol features excellent enantio- and diastereoselectivity, green and mild conditions, simple operation, and broad substrate scope, providing a modular platform for the synthesis of secondary axially chiral alcohols.

show abstract

Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

Cited by 57 publications

References 79 publications

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Allenyl Radicals in Organic Synthesis: Challenges and Recent Advances

Visible light-mediated cobalt and photoredox dual-catalyzed asymmetric reductive coupling of biaryl dialdehydes and aryl iodides

Contact Info

Product

Resources

About