Construction of Chiral Tri‐ and Tetra‐Arylmethanes Bearing Quaternary Carbon Centers: Copper‐Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters

Tsuchida, Kouhei; Senda, Yasushi; Nakajima, Kazunari; Nishibayashi, Yoshiaki

doi:10.1002/anie.201604182

Cited by 137 publications

(47 citation statements)

References 97 publications

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“…Figure 1 b indicates that electron-rich phosphines are superior to electron-deficient phosphines possibly because electron-rich phosphine can facilitate the cleavage of the propargylic C–O bond when Cu-2 is converted to Cu-3 . Unlike other copper-catalyzed propargylation methods performed in aprotic solvents, 25 − 29 polydentate ligands did not accelerate the reaction in water in this study. Therefore, the copper-catalyzed propargylic C–O bond cleavage in water requires different ligand design principles.…”

Section: Results and Discussioncontrasting

confidence: 77%

Using Ligand-Accelerated Catalysis to Repurpose Fluorogenic Reactions for Platinum or Copper

et al. 2020

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The development of a fluorescent probe for a specific metal has required exquisite design, synthesis, and optimization of fluorogenic molecules endowed with chelating moieties with heteroatoms. These probes are generally chelation- or reactivity-based. Catalysis-based fluorescent probes have the potential to be more sensitive; however, catalytic methods with a biocompatible fluorescence turn-on switch are rare. Here, we have exploited ligand-accelerated metal catalysis to repurpose known fluorescent probes for different metals, a new approach in probe development. We used the cleavage of allylic and propargylic ethers as platforms that were previously designed for palladium. After a single experiment that combinatorially examined >800 reactions with two variables (metal and ligand) for each ether, we discovered a platinum- or copper-selective method with the ligand effect of specific phosphines. Both metal–ligand systems were previously unknown and afforded strong signals owing to catalytic turnover. The fluorometric technologies were applied to geological, pharmaceutical, serum, and live cell samples and were used to discover that platinum accumulates in lysosomes in cisplatin-resistant cells in a manner that appears to be independent of copper distribution. The use of ligand-accelerated catalysis may present a new blueprint for engineering metal selectivity in probe development.

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Section: Results and Discussioncontrasting

confidence: 77%

Using Ligand-Accelerated Catalysis to Repurpose Fluorogenic Reactions for Platinum or Copper

et al. 2020

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“…77 The reaction proceeded under mild reaction conditions with high efficiency and excellent regioselectivity. Low yields were only observed when other conventional diamine ligands (111)(112)(113)(114)(115)(116)(117) were used along with the nickel catalyst, Fig. 3.…”

Section: Nickel Derived Catalystsmentioning

confidence: 99%

“…Nishibayashi and co-workers in the year 2016 developed a copper-catalyzed enantioselective propargylation of indoles 61 with propargylic esters 185, Scheme 81. 111 Treatment of 1,1,1-triuoro-2-phenylbut-3-yn-2-yl per-uorobenzoate 185 with indole 61 in the presence of 5 mol% of CuOTf$1/2C 6 H 6 and 10 mol% of (4S,5R)-diPh-Pybox 187a and N,N-diisopropylethylamine in methanol at room temperature for 1 hour furnished the desired propargyl substituted product 186 in 41% yield with 47% ee. Propargylic esters such as acetate and tert-butyl carbonate were unable to react under this reaction condition.…”

Section: Copper Derived Catalystsmentioning

confidence: 99%

Scope and advances in the catalytic propargylic substitution reaction

Roy

Saha

2018

RSC Adv.

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“…Nishibayashi and co-workers developed copper catalyzed enantioselectivep ropargylationo fi ndoles with propargylic esters followed by Huisgen 1, 3-dipolarc ycloaddition with azides for the enantioselective synthesis of triarylmethanes containing quaternary stereocenters (Scheme 49). [82] With the use of (4S, 5R)-diPh-Pybox (35) as the chiral ligand high yields and enantioselectivity can be achieved (up to 86 %y ield and 97 % ee). The authors could further extend this methodology for the enantioselective synthesis of tetraaryl methanes.…”

Section: Metal Catalysismentioning

confidence: 99%

Overview on the Recent Strategies for the Enantioselective Synthesis of 1, 1‐Diarylalkanes, Triarylmethanes and Related Molecules Containing the Diarylmethine Stereocenter

2018

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There has recently been an increased interest in active pharmaceutical agents and various other molecules that contain the 1, 1‐diaryl stereocenter. This has led to the development of novel synthetic strategies to access molecules having this structural moiety. The current Review describes the variety of synthetic methodologies available for the enantioselective synthesis of 1, 1‐diarylethanes, triarylmethanes and related molecules with a 1, 1‐diaryl stereogenic center that were reported since 1995. The prime focus of the Review is on the formation of the 1, 1‐diarylmethine stereocenter either through the use of various enantioselective processes using chiral catalysts (the asymmetric catalytic approach) or through the use of chiral substrates and achiral catalysts. Resolution of racemic substrates is also required for the synthesis of this chiral molecule, but this approach is not covered in this Review. Moreover, comparative discussions on the future aspects of the synthesis of these molecules with a short comparison of the different available routes and possible areas of development are also presented.

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Construction of Chiral Tri‐ and Tetra‐Arylmethanes Bearing Quaternary Carbon Centers: Copper‐Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters

Cited by 137 publications

References 97 publications

Using Ligand-Accelerated Catalysis to Repurpose Fluorogenic Reactions for Platinum or Copper

Using Ligand-Accelerated Catalysis to Repurpose Fluorogenic Reactions for Platinum or Copper

Scope and advances in the catalytic propargylic substitution reaction

Overview on the Recent Strategies for the Enantioselective Synthesis of 1, 1‐Diarylalkanes, Triarylmethanes and Related Molecules Containing the Diarylmethine Stereocenter

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