Copper-Catalyzed Enantioselective C–H Arylation between 2-Arylindoles and Hypervalent Iodine Reagents

Liu, Hao; Zhu, Guoxun; Pu, Xiaoyun; Qiu, Liqin

doi:10.1021/acs.orglett.1c03596

Cited by 12 publications

(10 citation statements)

References 57 publications

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“…We will illustrate that IGMH displays conspicuously better graphical effect than IGM in many cases, not only the isosurfaces are easier to visually inspect, but also possible misleading conclusion on the interaction type could be fully avoided. Due to the appealing feature of IGMH, this method has already been employed in some researches by Multiwfn users [27][28][29][30][31] since it was available in Multiwfn 3.7. Moreover, IGMH has a more rigorous physical basis than IGM, because it is defined on the top of actual molecular density rather than promolecular density, the latter one fully neglects electron transfer and polarization during formation of current system from isolated atoms.…”

Section: Introductionmentioning

confidence: 99%

Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems

Tian¹,

Chen²

2022

J Comput Chem

1,520

568

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The powerful independent gradient model (IGM) method has been increasingly popular in visual analysis of intramolecular and intermolecular interactions in recent years. However, we frequently observed that there is an evident shortcoming of IGM map in graphically studying weak interactions, that is its isosurfaces are usually too bulgy; in these cases, not only the graphical effect is poor, but also the color on some areas on the isosurfaces is inappropriate and may lead to erroneous analysis conclusions. In addition, the IGM method was originally proposed based on promolecular density, which is quite crude and does not take actual electronic structure into account. In this article, we propose an improvement version of IGM, namely IGM based on Hirshfeld partition of molecular density (IGMH), which replaces the free-state atomic densities involved in the IGM method with the atomic densities derived by Hirshfeld partition of actual molecular electron density. This change makes IGM have more rigorous physical background. A large number of application examples in this article, including molecular and periodic systems, weak and chemical bond interactions, fullydemonstrate the important value of IGMH in intuitively understanding interactions in chemical systems. Comparisons also showed that the IGMH usually has markedly better graphical effect than IGM and overcomes known problems in IGM. Currently IGMH analysis has been supported in our wavefunction analysis code Multiwfn (http://sobereva.com/multiwfn). We hope that IGMH will become a new useful method among chemists for exploring interactions in wide variety of chemical systems.

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Section: Introductionmentioning

confidence: 99%

Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems

Tian¹,

Chen²

2022

J Comput Chem

1,520

568

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“…A plausible reaction pathway for the copper-catalyzed onepot reaction is proposed on the basis of our experimental outcomes and previous reports (Scheme 4). [2,24] Cu(I)OTf A could be generated through disproportionation or reduction of Cu(OTf) 2 by an indole substrate. Then the oxidative addition of diaryliodonium salt provided aryl-Cu(III) species B which would afford C upon nucleophilic attack of the indole from C3 position.…”

Section: Resultsmentioning

confidence: 99%

Copper‐Catalyzed One‐Pot Arylation and Cyclization of Diaryliodonium Salts Derived fromo‐Iodoanilines for Indolo[2,3‐b]indoles Syntheses

2023

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One‐pot synthesis of various indolo[2,3‐b]indoles has been accomplished from a copper‐catalyzed transformation of easily accessible 2‐(substituted‐amino)aryl)(mesityl)iodonium salts and indole derivatives. Reaction offers great functional group toleration, providing a series of indolo[2,3‐b]indole derivatives in good yields. Additionally, intramolecular cyclization of 2‐(substituted‐amino)aryl)(mesityl)iodonium salts in the presence of copper‐catalyst provided direct access to benzoxazole derivatives.

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“…Interestingly, the potential of the Cu/Box-catalytic system in combination with hypervalent iodine is not limited to the synthesis of the C–N atropisomeric compounds. Recently, a closely related protocol was used to promote atroposelective C3-arylation of indoles, thus furnishing C–C atropisomeric compounds …”

Section: C–n Atropisomerism: Intriguing Chirality Elementmentioning

confidence: 99%

“…Recently, a closely related protocol was used to promote atroposelective C3-arylation of indoles, thus furnishing C−C atropisomeric compounds. 56 Even though atroposelective metal-catalyzed N-arylation still remains a niche topic, several intramolecular transformations have been recently reported. In 2019 Gu and co-workers reported a new Cu/N,N′-(cyclohexane-1,2-diyl) dipicolinamide catalyst for an intramolecular Ullmann-type C−N coupling occurring with concomitant control of the stereochemistry of the N−Ar bond.…”

Section: Elementmentioning

confidence: 99%

Sulfoxide-Directed or 3d-Metal Catalyzed C–H Activation and Hypervalent Iodines as Tools for Atroposelective Synthesis

Choppin

Wencel‐Delord

2023

Acc. Chem. Res.

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Conspectus The expanding applications of atropisomeric compounds combined with the growing diversity of such chiral molecules translate into an urgent need for innovative synthetic strategies allowing their rapid, efficient, and sustainable synthesis. Recently, the C–H activation approach has provided new opportunities for synthesizing axially chiral compounds. The two complementary approaches allowing implementation of the C–H activation methodology toward the synthesis of the chiral molecules imply either ortho-functionalization of the preexisting prochiral or atropo-unstable biaryl substrates or direct C–H arylation of sterically encumbered aromatics. The first approach required the preinstallation of a directing group on a biaryl precursor, which drastically limits the diversity of thus generated products. To tackle this important synthetic limitation, we have envisioned using a chiral sulfoxide as both directing group and chiral auxiliary. Indeed, in addition to efficiently coordinating the Pd-catalyst thus allowing chiral induction, the sulfoxide moiety can be easily removed, via the sulfoxide/lithium exchange, after the C–H activation step, thus guaranteeing an almost unlimited postdiversification of the atropisomeric products. The efficiency and generality of this concept could be illustrated by developing atropo-diastereoselective oxidative Heck reaction, direct acetoxylation, and iodination, as well as direct arylation. Besides, the synthetic utility of this methodology was demonstrated by designing an expedient synthesis of a direct steganone precursor. This unique transformation also allowed us to build up unprecedented triaryl scaffolds with two perfectly controlled chiral axes, original chiral skeletons for new ligand design. While considering the atroposelective direct arylations, the clear antagonism between the harsh reaction conditions frequently required for the coupling of two sterically hindered compounds and the atropo-stability of the new product, resulted in the scarcity of such transformations. To solve this fundamental challenge, we have focused on the application of a low-valent cobalt catalyst, prompted to catalyze C–H activation of indoles at the C2 position under extremely mild reaction conditions (room temperature). Accordingly, atroposelective C2-arylation of indoles could be achieved using an original carbene ligand and delivering the uncommon atropoisomerically pure indoles in excellent yields and enantioselectivities. Detailed combined experimental and theoretical mechanistic studies shed light on the mechanism of this transformation, providing strong evidence regarding the origin of the enantioselectivity. Finally, the antagonism between steric hindrance required to guarantee the atropo-stability of a molecule and harsh reaction conditions required to couple two partners is a strong limitation not only for the development of atroposelective C–H arylation reaction but also for the development of direct synthesis of the C–N axially chiral compounds. Despite the long history and i...

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Copper-Catalyzed Enantioselective C–H Arylation between 2-Arylindoles and Hypervalent Iodine Reagents

Cited by 12 publications

References 57 publications

Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems

Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems

Copper‐Catalyzed One‐Pot Arylation and Cyclization of Diaryliodonium Salts Derived fromo‐Iodoanilines for Indolo[2,3‐b]indoles Syntheses

Sulfoxide-Directed or 3d-Metal Catalyzed C–H Activation and Hypervalent Iodines as Tools for Atroposelective Synthesis

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