Molybdenum-Catalyzed Directed Activation of Aryl Chlorides and Fluorides

Somsuvra Banerjee; Naoki Matsushita; Eiichi Nakamura; Nitin T. Patil; Sobi Asako; Laurean Ilies

doi:10.1055/a-2187-9441

Synlett, Table of Contents

Synlett 2024; 35(10): 1141-1144
DOI: 10.1055/a-2187-9441

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Thieme Chemistry Journals Awardees 2023

Molybdenum-Catalyzed Directed Activation of Aryl Chlorides and Fluorides

Somsuvra Banerjee

^aRIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

,

Naoki Matsushita

^aRIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

^bDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

,

Eiichi Nakamura

^bDepartment of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

,

Nitin T. Patil

^cDepartment of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, India

,

Sobi Asako ∗

^aRIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

,

Laurean Ilies ∗

^aRIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

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Abstract

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Abstract

A low-valent molybdenum species generated by the reduction of a molybdenum precursor with phenylmagnesium bromide catalytically cleaves a C–Cl or C–F bond in an aromatic ketone under mild conditions, followed by cyclization to produce a hydroxyphthalan (1,3-dihydro-2-benzofuran-1-ol) derivative.

Key words

molybdenum catalysis - chloroarenes - fluoroarenes - phthalans - benzofuranols - cyclization

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References

References and Notes
1 Smedley PL, Kinniburgh DG. Appl. Geochem. 2017; 84: 387
2 Schwarz G, Mendel RR, Ribbe MW. Nature 2009; 460: 839

3a Catalysis Without Precious Metals . Bullock RM. Wiley-VCH; Weinheim: 2010
3b Nakamura E, Sato K. Nat. Mater. 2011; 10: 158
3c Bullock RM, Chen JG, Gagliardi L, Chirik PJ, Farha OK, Hendon CH, Jones CW, Keith JA, Klosin J, Minteer SD, Morris RH, Radosevich AT, Rauchfuss TB, Strotman NA, Vojvodic A, Ward TR, Yang JY, Surendranath Y. Science 2020; 369: eabc3183

4a Sousa SC. A, Fernandes AC. Coord. Chem. Rev. 2015; 284: 67
4b Nitrogen Fixation . Nishibayashi Y. Springer; Heidelberg: 2017
4c Molybdenum: An Outline of its Chemistry and Uses . Braithwaite ER, Haber J. Elsevier; Amsterdam: 2018

5a Metal-Catalyzed Cross-Coupling Reactions and More, Vol. 1–3. de Meijere A, Brässe S, Oestreich M. Wiley-VCH; Weinheim: 2014
5b Applied Cross-Coupling Reactions . Nishihara Y. Springer; Berlin: 2013

6a Sangu K, Watanabe T, Takaya J, Iwasawa N. Synlett 2007; 929
6b Ren W, Yamane M. J. Org. Chem. 2010; 75: 3017
6c Roberts B, Liptrot D, Alcaraz L, Luker T, Stocks MJ. Org. Lett. 2010; 12: 4280
6d Roberts B, Liptrot D, Luker T, Stocks MJ, Barber C, Webb N, Dods R, Martin B. Tetrahedron Lett. 2011; 52: 3793

7a Takaya J, Sangu K, Iwasawa N. Angew. Chem. Int. Ed. 2009; 48: 7090
7b Nakka M, Tadikonda R, Nakka S, Vidavalur S. Adv. Synth. Catal. 2016; 358: 520

For coupling of 2-iodoglycals, see:

7c Darbem MP, Esteves HA, Burrow RA, Soares-Paulino AA, Pimenta DC, Stefani HA. RSC Adv. 2022; 12: 2145

8a Kiplinger JL, Richmond TG. Polyhedron 1997; 16: 409
8b Himmelbauer D, Mastalir M, Stöger B, Veiros LF, Kirchner K. Organometallics 2018; 37: 3631

9a Grushin VV, Alper H. Chem. Rev. 1994; 94: 1047
9b Littke AF, Fu GC. Angew. Chem. Int. Ed. 2002; 41: 4176

10 Keller MB. J. Clin. Psychiatry (Memphis, TN U. S.) 2000; 61: 896

11a Asako S, Ishikawa S, Takai K. ACS Catal. 2016; 6: 3387
11b Asako S, Sakae T, Murai M, Takai K. Adv. Synth. Catal. 2016; 358: 3966

12 Asako S, Kobashi T, Takai K. J. Am. Chem. Soc. 2018; 140: 15425

13a Asako S, Ishihara S, Hirata K, Takai K. J. Am. Chem. Soc. 2019; 141: 9832
13b Asako S, Kobayashi T, Ishihara S, Takai K. Asian J. Org. Chem. 2021; 10: 753
13c Banerjee S, Kobayashi T, Takai K, Asako S, Ilies L. Org. Lett. 2022; 24: 7242

14a Shang R, Ilies L, Nakamura E. Chem. Rev. 2017; 117: 9086
14b Ilies L. Bull. Chem. Soc. Jpn. 2021; 94: 404

15 CCDC 2270774 contains the supplementary crystallographic data for compound 2a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures

For examples, see:

16a Cahiez G, Luart D, Lecomte F. Org. Lett. 2004; 6: 4395
16b Sapountzis I, Lin W, Kofink CC, Despotopoulou C, Knochel P. Angew. Chem. Int. Ed. 2005; 44: 1654
16c Korn TJ, Knochel P. Angew. Chem. Int. Ed. 2005; 44: 2947
16d Korn TJ, Schade MA, Cheemala MN, Wirth S, Guevara SA, Cahiez G, Knochel P. Synthesis 2006; 3547
16e Steib AK, Kuzmina OM, Fernandez S, Flubacher D, Knochel P. J. Am. Chem. Soc. 2013; 135: 15346
16f Zeng J, Liu KM, Duan XF. Org. Lett. 2013; 15: 5342
16g Hua X.-Y, Masson-Makdissi J, Sullivan RJ, Newman SG. Org. Lett. 2016; 18: 5312

17 Hydroxyphthalans 2a–e; General Procedure MoO₂Cl₂(dtbpy) (4.6 mg, 0.010 mmol, 2 mol%) and the appropriate 2-halobenzophenone 1 (0.50 mmol) were added to a dry Schlenk tube equipped with a Teflon-coated magnetic stirrer bar under a N₂ atmosphere. The reaction vessel was fitted with a rubber septum and charged with THF (0.50 mL) from a syringe. The mixture was stirred until a clear light-pinkish solution formed, then cooled to 0 °C (ice bath). Next, a 0.81 mol/L solution of PhMgBr in THF (0.74 mL, 1.2 equiv) was added dropwise by using a syringe pump (addition rate: 0.5 mL/min) at 0 °C under nitrogen. Upon addition, the color of the reaction mixture turned deep violet. After completion of the addition, the septum was removed, the Schlenk tube was sealed under N₂ with a screw cap, and the mixture was stirred at rt for 16 h. Tridecane, as an internal standard for GC, and THF (~0.5 mL) were added, and the resulting mixture was stirred vigorously for 5 min. The reaction was then quenched by the addition of a sat. aq NH₄Cl (~1 mL) and 30% aq potassium sodium tartrate (~1 mL) with continuous stirring for 5 min. An aliquot was taken directly from the upper organic layer and passed through a plug of Florisil with EtOAc. The resulting solution was analyzed by GC to determine the yield. The aliquot for GC measurement was then returned to the reaction mixture, which was extracted with EtOAc. The combined organic phase was passed through a plug of Florisil, dried (Na₂SO₄), and then concentrated under reduced pressure. The resulting mixture was analyzed by ¹H or ¹⁹F NMR to estimate the yield. The product was finally isolated by column chromatography on neutral alumina. 3-(2-Chlorophenyl)-1,3-diphenyl-1,3-dihydro-2-benzofuran-1-ol (2a) Two batches were prepared in by the general procedure from 1a [213.6 mg, (0.98 mmol) and 211.6 mg (0.97 mmol)]. During workup, the two batches were combined, and the yield (89%) was determined by GC analysis. Purification by column chromatography (neutral alumina; 10% EtOAc–hexane) gave a colorless solid; yield: 323.9 mg (83%, 0.81 mmol). Minor impurities were removed by further purification by GPC (CHCl₃). The diastereoselectivity of the product was 1.1:1. ¹H NMR (500 MHz, CDCl₃): δ = 7.65–7.59 (m, 3 H), 7.55 (dt, J = 7.7, 0.8 Hz, 1 H), 7.53–7.49 (m, 2 H), 7.48–7.27 (m, 27 H), 7.24–7.22 (m, 3 H), 7.15 (td, J = 7.6, 1.3 Hz, 1 H), 3.52 (s, 1 H), 3.07 (s, 1 H). ¹³C{1 H} NMR (126 MHz, CDCl₃): δ = 145.7, 143.8, 143.5, 143.0, 142.85, 142.80, 142.5, 142.3, 142.0, 140.64, 134.9, 133.9, 132.2, 132.1, 129.7, 129.5, 129.4, 129.27, 129.25, 129.0, 128.9, 128.6, 128.5, 128.4, 128.35, 128.31, 127.4, 127.2, 126.6, 126.5, 126.3, 126.08, 126.04, 125.7, 125.0, 124.7, 123.78, 123.66, 108.5, 107.8, 93.90, 92.6. HRMS (APCI⁺): m/z [M – OH]⁺ calcd for C₂₆H₁₈ClO: 381.1041; found: 381.1020.

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