Rhodium-Catalyzed Atroposelective Oxidative C–H/C–H Cross-Coupling Reaction of 1-Aryl Isoquinoline Derivatives with Electron-Rich Heteroarenes

Wang, Qiang; Zhang, Wen; Song, Hao; Wang, Jian; Zheng, Chao; Gu, Qianqun; You, Shu‐Li

doi:10.1021/jacs.0c08205

Cited by 158 publications

(62 citation statements)

References 149 publications

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“…Having established the optimal reaction conditions, we next examined the scope of the arene substrates (Scheme 2). Symmetric diarylphosphinic amides bearing an electron-donating (Me, Et, t Bu, OEt, and OMe), -withdrawing (Ph and CF3), and halogen groups at the para position of the benzene ring were generally well tolerated, and the corresponding products (4)(5)(6)(7)(8)(9)(10)(11)(12)(13) were isolated in moderate to good yields and in 93.5:6.5 to 97.5:2.5 e.r. Arenes bearing meta alkyl and alkoxyl groups were also compatible (14)(15)(16)(17), and the C-H activation took place at the less hindered ortho C-H site in excellent enantioselectivity (95.5:4.5 to 97:3 e.r.).…”

Section: Resultsmentioning

confidence: 99%

“…The procedure to obtain the respective phosphines was adapted from literature [9][10][11][12] and was further modified to give the desired phosphine oxides.…”

Section: General Proceduresmentioning

confidence: 99%

“…[10] Werecently applied oalkynylaniline as an arylating reagent for 2,3'-biindolyl synthesis. [11] In 2020, You [12] achieved arylation of arenes via dynamic kinetic transformation of arenes using heteroarenes as an arylating reagent. Despite the progress, generation of axial chirality calls for employment of more readily available arylating reagents.…”

Section: Introductionmentioning

confidence: 99%

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Twofold C−H Activation‐Based Enantio‐ and Diastereoselective C−H Arylation Using Diarylacetylenes as Rare Arylating Reagents

Hu,

Kong,

Wang

et al. 2021

Angew Chem Int Ed

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C-H bond activation has been established as an attractive strategy to access axially chiral biaryls, and the most straightforward method is direct C-H arylation of arenes. However, the arylating source has been limited to several classes of reactive and bulky reagents. Reported herein is rhodium-catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes for enantio-and diastereoselective construction of biaryls with both central and axial chirality. This twofold C-H activation reaction stays contrast to the previously explored Miura-Satoh type 1:2 coupling of arenes and alkynes in terms of chemoselectivity and proceeded under mild conditions with the alkyne acting as a rare arylating reagent. Both C-H activation events are stereo-determining and are under catalyst control, with the 2 nd C-H activation being diastereo-determining in a remote fashion. Analysis of the stereochemistries of the major and side products suggests moderated enantioselectivity of the initial C-H activation-desymmetrization process. However, the minor stereoisomeric (R) intermediate is consumed more readily in undesired protonolysis, eventually resulting in high enantio-and diastereoselectivity of the major product. File list (2) download file view on ChemRxiv manuscript.pdf (656.75 KiB) download file view on ChemRxiv SI.pdf (4.50 MiB)

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Section: Resultsmentioning

confidence: 99%

“…The procedure to obtain the respective phosphines was adapted from literature [9][10][11][12] and was further modified to give the desired phosphine oxides.…”

Section: General Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Twofold C−H Activation‐Based Enantio‐ and Diastereoselective C−H Arylation Using Diarylacetylenes as Rare Arylating Reagents

Hu,

Kong,

Wang

et al. 2021

Angew Chem Int Ed

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“…The stereochemical stabilities of our axially chiral styrenes were evaluated via both experimental and computational methods. [67][68][69][70] We monitored the ee value of 9a over 24 h at different temperatures in toluene, and found 9a racemerized quickly at 100 o C, but much slower at 75 o C and 50 o C (Fig. 2a).…”

Section: Resultsmentioning

confidence: 99%

Carbene-Catalyzed Atroposelective Synthesis of Axially Chiral Styrenes Bearing Acyclic Alkenes

Jia

Maiti

Ren

et al. 2021

Preprint

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Axially chiral styrenes bearing a chiral axis between a sterically non-congested acyclic alkene and an aryl ring are difficult to prepare due to low rotational barrier of the axis. Disclosed here is an N-heterocyclic carbene (NHC) catalytic asymmetric solution to this problem. Our reaction involves ynals, sulfinic acids, and phenols as the substrates with an NHC as the catalyst. Key steps involve selective 1,4-addition of sulfinic anion to acetylenic acylazolium intermediate and sequential E-selective protonation to set up the chiral axis. Our reaction affords axially chiral styrenes bearing a chiral axis as the product with up to >99:1 e.r., >20:1 E/Z selectivity, and excellent yields. The sulfone and carboxylic ester moieties in our styrene products are common moieties in bioactive molecules and asymmetric catalysis.

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“…Nd:YAG laser pulses with a width of microseconds and 1064 nm wavelength are useful for treating keloid, hypertrophic or surgical scars. Moreover, millisecond laser pulses have been used extensively in laser machining, e.g., for cutting, welding and drilling of machinery materials throughout the fields of automobile, shipbuilding and aerospace industries [7–9] . Recently, the high-energy laser system with pulse shaping techniques from nanosecond to millisecond timescales has been actively studied for these applications [10] .…”

Section: Introductionmentioning

confidence: 99%

Optimization of the pulse width and injection time in a double-pass laser amplifier

Park

Jeong

2018

High Pow Laser Sci Eng

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We have optimized the input pulse width and injection time to achieve the highest possible output pulse energy in a double-pass laser amplifier. For this purpose, we have extended the modified Frantz-Nodvik equation [1] by simultaneously including both spontaneous emission and pump energy variation. The maximum achieved fluence of the output pulse was 2.4 J/cm 2 . An input pulse energy of 1 J could be maximally amplified to output pulse energy of 12.17 J, where the optimal values of the pulse width and injection time of the input pulse were 168 and 10 , respectively, with the effective pump energy being 8.84 J.

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Rhodium-Catalyzed Atroposelective Oxidative C–H/C–H Cross-Coupling Reaction of 1-Aryl Isoquinoline Derivatives with Electron-Rich Heteroarenes

Cited by 158 publications

References 149 publications

Twofold C−H Activation‐Based Enantio‐ and Diastereoselective C−H Arylation Using Diarylacetylenes as Rare Arylating Reagents

Twofold C−H Activation‐Based Enantio‐ and Diastereoselective C−H Arylation Using Diarylacetylenes as Rare Arylating Reagents

Carbene-Catalyzed Atroposelective Synthesis of Axially Chiral Styrenes Bearing Acyclic Alkenes

Optimization of the pulse width and injection time in a double-pass laser amplifier

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