Photoinduced gold-catalyzed divergent dechloroalkylation of gem-dichloroalkanes

Ji, Chenglong; Han, Jie; Li, Tingrui; Zhao, Chuan‐Gang; Zhu, Chengjian; Xie, Jin

doi:10.1038/s41929-022-00881-5

Cited by 62 publications

(28 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…According to the above investigations and previous literature, 9,14,15,23 a plausible mechanistic pathway is outlined in Scheme 5. Initially, carboxylate anion A undergoes a SET-oxidation process with Cu II to produce the indole-3-methyl radical 67 with the formation of Cu I .…”

mentioning

confidence: 68%

Microwave-assisted copper catalyzed decarboxylative reductive coupling ofpara-quinone methides with 3-indoleacetic acids: rapid access to polycyclic spiroindolequinone derivatives

Song

Liu

et al. 2023

Org. Chem. Front.

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 68%

Microwave-assisted copper catalyzed decarboxylative reductive coupling ofpara-quinone methides with 3-indoleacetic acids: rapid access to polycyclic spiroindolequinone derivatives

Song

Liu

et al. 2023

Org. Chem. Front.

View full text Add to dashboard Cite

show abstract

“…When [Au 3 (tppm) 2 ](Cl) 3 ( PC2 ) was used, a lower yield of 60 % was obtained (entry 2). Although the [Au(dppm)Cl] 2 ( PC3 ) and [Au(dcpm)Cl] 2 ( PC4 ) have been reported in SET reactions of unactivated organic halides successfully, [4b, 6a,d, 9e, 14] only low yields of 29–31 % were obtained when either PC3 or PC4 was used as photocatalyst (Table 1, entries 3 and 4). We envisioned that [Au 3 (tppm) 2 ](OTf) 3 ( PC1 ) strikes a good balance between reducing and oxidizing ability during the RPC process, and thus can efficiently oxidize the generating benzylic radical to a benzyl cation.…”

Section: Resultsmentioning

confidence: 99%

Trinuclear Gold‐Catalyzed 1,2‐Difunctionalization of Alkenes

et al. 2023

Self Cite

View full text Add to dashboard Cite

Activated alkyl halides have been extensively explored to generate alkyl radicals with Ru‐ and Ir‐ photocatalysts for 1,2‐difunctionalization of alkenes, but unactivated alkyl bromides remain challenging substrates due to their strong reduction potential. Here we report a three‐component 1,2‐difunctionalization reaction of alkenes, unactivated alkyl bromides and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au3(tppm)2](OTf)3. It can achieve the 1,2‐aminoalkylation and 1,2‐alkylarylation readily. This protocol has a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96 % yield). It also affords a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner‐sphere single electron transfer pathway for the successful cleavage of inert C−Br bonds.

show abstract

“…Although the non‐linear effect study supports pathway a , we could not exclude the possibility of pathway b . Meanwhile, it is also plausible that the α‐chloro alkyl radical directly adds to the terminal olefins 2 a to give a new radical, followed by the interception with Cr II / L1 and concerted ring‐closure [13d,f] …”

Section: Resultsmentioning

confidence: 99%

Catalytic Diastereo‐ and Enantioselective Cyclopropanation of gem‐Dihaloalkanes and Terminal Olefins

et al. 2023

View full text Add to dashboard Cite

Chiral cyclopropane derivatives are essential in synthetic chemistry and drug discovery. Their synthesis commonly relies on asymmetric cyclopropanation of diazo compounds, potentially explosive and needing stabilizing substituents. Thus, asymmetric catalytic transformations of non-stabilized carbenes or carbenoids remain a formidable challenge. Herein, we report the unprecedented chromium-catalyzed asymmetric cyclopropanation of readily available gem-dihaloalkanes and terminal olefins. Distinct from previous approaches, gem-dihaloalkanes serve as suitable precursors for nonstabilized carbenes or carbenoids, furnishing various functionalized chiral cyclopropanes. Mechanistic studies, including radical trapping, non-linear effect, and UV/Vis spectroscopy, provide insights into the catalytic process, featuring radical-polar crossover.

show abstract

Photoinduced gold-catalyzed divergent dechloroalkylation of gem-dichloroalkanes

Cited by 62 publications

References 57 publications

Microwave-assisted copper catalyzed decarboxylative reductive coupling ofpara-quinone methides with 3-indoleacetic acids: rapid access to polycyclic spiroindolequinone derivatives

Microwave-assisted copper catalyzed decarboxylative reductive coupling ofpara-quinone methides with 3-indoleacetic acids: rapid access to polycyclic spiroindolequinone derivatives

Trinuclear Gold‐Catalyzed 1,2‐Difunctionalization of Alkenes

Catalytic Diastereo‐ and Enantioselective Cyclopropanation of gem‐Dihaloalkanes and Terminal Olefins

Contact Info

Product

Resources

About