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Simultaneous Construction of Axial and Planar Chirality by Gold/TY

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Simultaneous Construction of Axial and Planar Chirality by Gold/TY ARTICLE https://doi.org/10.1038/s41467-021-24678-5 OPEN Simultaneous construction of axial and planar chirality by gold/TY-Phos-catalyzed asymmetric hydroarylation ✉ ✉ ✉ Pei-Chao Zhang 1, Yin-Lin Li 1, Jiafeng He 1, Hai-Hong Wu 1 , Zhiming Li2 & Junliang Zhang 2,3 The simultaneous construction of two different chiralities via a simple operation poses considerable challenge. Herein a cationic gold-catalyzed asymmetric hydroarylation of ortho- 1234567890():,; alkynylaryl ferrocenes derivatives is developed, which enable the simultaneous construction of axial and planar chirality. The here identified TY-Phos derived gold complex is responsible for the high yield, good diastereoselectivity (>20:1 dr), high enantioselectivities (up to 99% ee) and mild conditions. The catalyst system also shows potential application in the synthesis of chiral biaryl compounds. The cause of high enantioselectivity of this hydroarylation is investigated with density functional theory caculation. 1 Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China. 2 Department of Chemistry, Fudan University, Shanghai, China. 3 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of ✉ Organic Chemistry, CAS, Shanghai, China. email: [email protected]; [email protected]; [email protected] NATURE COMMUNICATIONS | (2021) 12:4609 | https://doi.org/10.1038/s41467-021-24678-5 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24678-5 s an effective and exceptionally versatile strategy, the undergo a related asymmetric desymmetric aromatization, and development of catalytic asymmetric intramolecular (3) the inherent difficulties to asymmetric gold catalysis, which A 1–10 hydroarylation for the construction of axial and stem from its linear coordination geometry and the outer-sphere planar11–13 chirality or helicenes14–20 has received much nature of Au(I)-catalysis44–50. To test our hypothesis, our inves- attention21–32. Various transition metal catalysis involving Au, Pt, tigation began with the cyclization of ortho-alkynylaryl ferrocene Rh, and Pd, have been reported in this regard. For instance, the derivative 1aa. A series of commercially available chiral ligands groups of Alcarazo1,14,16,18 and Tanaka6,15,17 extensively studied were investigated (please find more details in the Supplementary the Au-catalyzed and Rh-catalyzed intramolecular alkyne Information (SI) Supplementary Fig. S3). Unfortunately, catalysts hydroarylation to achieve enantioselective synthesis of axially used by Urbano-Carreño11, Shibata12, or Uemura10 all failed to chiral biaryls and helicenes, respectively (Fig. 1a). In 2013, give the desired cyclization product (Fig. 2, entries 1–3). (R)- Uemura et al.10 developed a Pd-catalyzed asymmetric cycloi- DTBM-SEGPhos (L1), the commonly used chiral ligand in somerization of enynes for the construction of axially chiral asymmetric gold catalysis, delivered the enantiomer of 2aa in 15% biaryl. The group of Urbano and Carreño11 developed an Au- NMR yield with 80% ee and 3:1 diastereoselectivity. (S,S)-Ph-BPE catalyzed cyclization to construct the planar naphthalene-fused (L2) could give the product 2aa in quite low enantioselectivity ferrocenes in 2016 (Fig. 1a). Later, Shibata et al.12 reported the and conversion. (R)-BINAP (L3) furnished 2aa in 62% NMR similar reaction enabled by a Pt-catalysis. Meanwhile, the capacity yield with 51% ee and 5:1 d.r., and the dominant Brønsted acid of intramolecular hydroarylation is impressively complemented (R)-CPA (L4) in the field of atroposelective synthesis of axially by various other versatile stereocontrolled methodologies. chiral molecules, cylohexanediamine-derived (S,S)-DACH-Phe- For example, Shibata2 and co-workers reported a Rh-catalysed nyl Trost Ligand (L5), (R)-BI-DIME (L6), Binol-derived phos- enantioselective synthesis of axially chiral PAHs via regioselective phor-amidite (Sa,R,R)-CPPA (L7), chiral oxazoline-phosphine cleavage of biphenylenes. Stará and Starý19,20 developed a ligand (R)-tBu-PHOX (L8), all have insufficient catalytic activity. Ni-catalysed enantioselective [2 + 2 + 2] cycloisomerisation We next turned to investigate our developed chiral sulfinamide of aromatic triynes to obtain the helicene derivatives. Toullec3, phosphine (Sadphos), which has shown good performance in Yan4, Irie5, and Sparr7–9 independently demonstrated efficient asymmetric gold catalysis41–43 (Sadphos are commercially avail- organocatalytic enantioselective cyclization of aryl-alkynes to able (Daicel and Strem), which are also easily prepared in construct valuable molecules containing axial or axial and helical 2–4 steps from chiral tert-butane sulfinamide.) (Fig. 2). The gold stereogenic elements. complexes derived from Ming-Phos42,43,54–56, Xu-Phos57–61, In this work, the simultaneous construction of axial and planar Xiang-Phos62–65, PC-Phos41,66–68 and TY-Phos69 could deliver chiralities is realized via the gold-catalyzed33–42 asymmetric (−)-2aa in up to 83% yield with 85% ee. We found that enan- intramolecular hydroarylation of readily available o- tioselectivity roughly correlates to the electrical properties of the alkynylferrocene derivatives 143 (Fig. 1c). And the simultaneous Sadphos, with a more σ-donating ligand providing a higher construction of two different types of chiralities is now flourishing enantioselectivity and catalytic activity. Notably, Au(TY-Phos)Cl development (Fig. 1b)44–51. could be easily synthesized in a gram scale via a five-steps in “one-pot” synthesis (for more details, see the SI). Inspired by this promising result, we varied the Ar group of TY-Phos (TY2–TY4) Results and introduced electron-donating groups to the aryl moiety of Optimization of the reaction conditions. However, to the best of TY-Phos, structured as TY5-TY6 with alkyl groups. Gratifyingly, our knowledge, simultaneous construction of multiple chiralities the product 2aa could be obtained in 83% yield with 85% ee and by asymmetric gold catalysis has not been reported so far, this 5:1 d.r. with the use of [Au(TY5)]BArF as the catalyst. Moreover, hypothesis faced considerable challenges: (1) the universal and N-Me-TY5 delivered much lower enantioselectivity to 46% ee efficient asymmetric intramolecular desymmetric cyclization for (Fig. 2, entry 10). Then, the effect of the counterion was inves- the construction of planar ferrocene derivatives was not well tigated (Fig. 2, entries 8, 11–13)70, among which sodium tetrakis − developed (In the work of refs. 11,12,10–20 mol% catalytic [3,5-bis(trifluoro-methyl) phenyl]borate (BArF ) delivered the loading was used), (2) on the other hand, simultaneous con- best enantioselectivity and reactivity. Subsequently, either low- struction of axial and planar chiral molecules via asymmetric ering the temperature to −10 °C or using other solvents such as catalysis has rarely been reported52,53 and innate reluctance to DCE and toluene failed to give better result (Fig. 2, entries 14–16). a Asymmetric intramolecular hydroarylation for arene formation b Simultaneous construction of two different types of chiralities 2 Asymmetric P* C6 Si* Hydroarylation Axial chirality Planar chirality Axial chirality Asymmetric catalysis Helicenes Helicenes Regioselectivity Planar chirality (Flourishing developed) Central chirality Desymmetrisation Stereoselective 1,3-Dien-5-ynes Arene Formation c Construction of Axial and Planar chirality (this work) R R' OR OR Fe R chiral Au cat. RO TY-Phos Axial-Planar chirality i) Axial chirality ii) Planar chirality iii) Helicenes Fe Fe Alcarazo, Tanaka Urbano & Carreño Alcarazo, Tanaka (Underdeveloped) Uemura Shibata 1 2 chiral Au, Rh, Pd cat. chiral Au, Pt cat. chiral Au, Rh cat. Fig. 1 Background and project synopsis. a Asymmetric intramolecular hydroarylation for arene formation. b Simultaneous construction of two different types of chiralities. c Construction of Axial and Planar chirality (this work). 2 NATURE COMMUNICATIONS | (2021) 12:4609 | https://doi.org/10.1038/s41467-021-24678-5 | www.nature.com/naturecommunications NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-021-24678-5 ARTICLE OMe Au(Sadphos)Cl (5 mol%) R O Add. (6 mol%) MeO S N tBu H o Fe DCM (0.1 M), 0 C Fe PR2 0.1 mmol, 1aa 2aa Sadphos Family Ar O R= Ph, Ar= 1-Naph, Au(Ming-Phos)Cl, 79%, 4% ee, 5:1 d.r R= Cy, Ar= 1-Naph, Au(Xu-Phos)Cl, 81%, 23% ee, 5:1 d.r S R= Ad, Ar= 1-Naph, Au(Xiang-Phos)Cl, 82%, 52% ee, 5:1 d.r N tBu H R= tBu, Ar= 1-Naph, Au(TY-Phos)Cl (TY1) t PR2AuCl R= Bu, Ar= Ph (TY2) t t R= Bu, Ar= 3,5- Bu2-4-MeO-Ph (TY3) R= tBu, Ar= PMP (TY4) Entry L* Add. Conv. [%] Yield [%]b,c Ee [%]b,c d.r.d 1 Urbano-Carreño's strategy < 5 trace _ _ 2 Shibata's strategy 0 NR _ _ _ _ 3 Uemura's strategy 0 NR F 4 TY1 NaBAr 100 80 83 5:1 F 5 TY2 NaBAr 100 79 42 5:1 6 TY3 NaBArF 100 82 76 5:1 7 TY4 NaBArF 100 83 48 5:1 8 TY5 NaBArF 100 83 85 5:1 9 TY6 NaBArF 100 83 62 5:1 10 N-Me-TY5 NaBArF 100 82 46 5:1 11 TY5 AgBF4 100 80 83 5:1 12 TY5 AgSbF6 80 66 81 3:1 13 TY5 AgNTf2 70 58 83 4:1 F 14 TY5 NaBAr 100 80 85 5:1 F _ 15 TY5 NaBAr < 10 trace _ TY5 NaBArF 16 50 83 43 5:1 _ _ 17 TY5 0 NR _ _ _ 18 NaBArF 0 NR _ 1-Naph Ar O O HN S S N tBu O tBu H t P Bu2AuCl PPh2AuCl Ar= 1-Naph (TY5) Au(PC-Phos)Cl Ar= 9-Anthryl (TY6) (Sc,Rs)-Au(TY-6)Cl 80%, 16% ee, 4:1 d.r CCDC 2052077 Fig. 2 Optimization of reaction conditions. aUnless otherwise noted, all reactions were carried out with 0.1 mmol of 1aa and 10 mol% of catalyst (Au: P: NaBArF (additive) = 1:1:1.2) in 1.0 mL DCM at 0 °C for 24 h; bIsolated yield.
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