4b-Aryltetrahydroindeno[1,2-a]indenes by Acid-Catalyzed Trans­annular Cyclization of Benzannulated Cyclooctene Alcohols

Dedicated to the late Professor Robert H. Grubbs

Abstract

By starting from two simple building blocks, benzannulated cyclooctenones were obtained in three steps. Subsequent Grignard/aryl lithium addition to the ketone yielded the corresponding tertiary alcohols that underwent stereoselective acid-catalyzed transannular cyclization to provide a cis-fused 5/5 bicyclic indanylindane framework exclusively. Subsequent stereoselective nucleophilic addition to the indanyl cation by hydride, water, or electron-rich aromatics furnished the 4b-aryltetrahydroindano[1,2-a]indenes in good to excellent yields (up to 92%) in the trans-C9–C9a form in up to a >99:1 diastereomeric ratio.

Key words

carbocations - cyclization - diastereoselectivity - metathesis - acid catalysis - indenoindenes

Publication History

Received: 22 January 2022

Accepted after revision: 22 February 2022

Accepted Manuscript online:
22 February 2022

Article published online:
28 April 2022

• References and Notes

• 1 Gallou I, Senanayake CH. Chem. Rev. 2006; 106: 2843
• 2 Gabriele B, Mancuso R, Veltri L. Chem. Eur. J. 2016; 22: 5056
• 3 Hashimoto T, Shimazaki Y, Omatsu Y, Maruoka K. Angew. Chem. Int. Ed. 2018; 57: 7200
• 4 Chan K, Frankish N, Zhang T, Ece A, Cannon A, O’Sullivan J, Sheridan H. J. Pharm. Pharmacol. 2020; 72: 927
• 5 Prasher P, Sharma M. ChemistrySelect 2021; 6: 2658
• 6 Johnston CP, Kothari A, Sergeieva T, Okovytyy SI, Jackson KE, Paton RS, Smith MD. Nat. Chem. 2015; 7: 171
• 7 Chen Y.-y, Chen Z.-y, Zhang N.-n, Chen J.-h, Zhang X.-j, Yan M. Eur. J. Org. Chem. 2016; 599
• 8 Ahmed N. Stud. Nat. Prod. Chem. 2016; 51: 383
• 9 Borie C, Ackermann L, Nechab M. Chem. Soc. Rev. 2016; 45: 1368
• 10 Zhang Z, Wang J, Li J, Yang F, Liu G, Tang W, He W, Fu J.-J, Shen Y.-H, Li A, Zhang W.-D. J. Am. Chem. Soc. 2017; 139: 5558
• 11 Wang D.-D, Wei Q.-D, Wang G.-L, Gong Y, Liu X.-L, Zhou G, Zhou Y, Zhang J.-F. Synth. Commun. 2018; 48: 1346
• 12a Sarnpitak P, Trongchit K, Kostenko Y, Sathalai S, Gleeson MP, Ruchirawat S, Ploypradith P. J. Org. Chem. 2013; 78: 8281
• 12b Jongcharoenkamol J, Chuathong P, Amako Y, Kono M, Poonswat K, Ruchirawat S, Ploypradith P. J. Org. Chem. 2018; 83: 13184
• 13 Hu W, Zhang C, Huang J, Guo Y, Fu Z, Huang W. Org. Lett. 2019; 21: 941 ; corrigendum: Org. Lett. 2019, 21, 2966
• 14 Khoroshilova OV, Vasilyev AV. Organics 2021; 2: 348
• 15 Chuen CC, Fenton SW. J. Org. Chem. 1958; 23: 1538
• 16 Sondheimer F, Gaoni Y. J. Am. Chem. Soc. 1961; 83: 4863
• 17 Fuchibe K, Mitomi K, Akiyama T. Chem. Lett. 2007; 36: 24
• 18 Sánchez-Larios E, Holmes JM, Daschner CL, Gravel M. Org. Lett. 2010; 12: 5772
• 19 Shim JY, Lee BH, Song S, Kim H, Kim JA, Kim I, Lee K, Suh H. J. Polym. Sci., Part A: Polym. Chem. 2013; 51: 241
• 20 Lekky A, Ruengsatra T, Ruchirawat S, Ploypradith P. J. Org. Chem. 2019; 84: 5277
• 21 Regardless of the nucleophile, the use of PTS-Si, In(OTf)₃, Bi(OTf)₃, PtCl₄, or BF₃·Et₂O, as the catalyst and CH₂Cl₂ or DCE as the solvent did not give the corresponding transannular cyclization products; only the products from nucleophilic addition at the benzylic position were obtained (See Supporting Information, Table S1).
• 22 Phumjan T, Songthammawat P, Jongcharoenkamol J, Batsomboon P, Ruchirawat S, Ploypradith P. J. Org. Chem. 2021; 86: 13322
• 23 4b-Phenyl-9-(2,4,6-trimethoxyphenyl)-4b,9,9a,10-tetrahydroindeno[1,2-a]indene (3b); Typical Procedure 1,3,5-Trimethoxybenzene (8.5 mg, 0.05 mmol) and PTS-Si (7.8 mg, 0.0063 mmol) were added sequentially to a solution of tertiary alcohol 4a (18.8 mg, 0.063 mmol) in DCE (0.50 mL) at r.t., and the mixture was heated at 60 °C with stirring for 4 h. The catalyst was filtered off and the mixture was concentrated under reduced pressure to give a crude product that was further purified by column chromatography (silica gel, 3–5% EtOAc–hexane) to give a white solid; yield: 17.9 mg (0.04 mmol, 83%). Major (M)/minor (m) = 1.64:1. ¹H NMR (300 MHz, CDCl₃): δ = 7.32–7.15 (m, 9 H), 7.08 (td, J = 7.3, 6.8, 1.7 Hz, 4 H), 7.02–6.97 (m, 1 H), 6.75 (d, J = 7.6 Hz, 1 H), 6.21 (br s, 2 H, M), 6.21 (br s, 1 H, m), 6.03 (br s, 1 H, m), 5.24 (d, J = 8.9 Hz, 1 H, m), 4.64 (d, J = 8.8 Hz, 1 H, M), 3.86 (s, 3 H, M), 3.85 (s, 3 H, m), 3.80 (br s, 3 H, M), 3.62 (br s, 3 H, M), 3.62 (br s, 6 H, m), 3.58–3.47 (m, 1 H, m), 3.58–3.47 (m, 2 H, m), 3.05–2.89 (m, 3 H, M). ¹³C{¹H} NMR (75 MHz, CDCl₃): δ = 59.9 (M), 159.8 (m), 149.3 (m), 148.9 (m), 148.7 (M), 148.4 (M), 148.4 (M), 147.1 (m), 145.5 (m), 145.4 (m), 145.3 (M), 143.9 (M), 128.0 (M), 127.9 (m), 127.8 (m), 127.7 (M), 126.9 (M), 126.8 (M), 126.4 (M), 126.2 (M), 126.1 (M), 125.9 (M), 125.8 (M), 125.8 (M), 125.7 (m), 125.5 (M), 124.9 (m), 124.8 (m), 124.5 (m), 124.2 (M), 123.9 (m), 122.4 (M), 111.8 (M), 109.4 (m), 70.4 (m), 69.6 (M), 62.4 (M), 59.1 (m), 55.3 (M), 55.2 (m), 45.8 (M), 42.4 (m), 35.2 (M), 34.0 (m). ESI-HRMS: m/z [M + Na]⁺ calcd for C₃₁H₂₈NaO₃: 471.1931; found: 471.1952.
• 24a Chang S.-J, McNally D, Shary-Tehrany S, Hickey MJ, Boyd RH. J. Am. Chem. Soc. 1970; 92: 3109
• 24b Gordon HL, Freeman S, Hudlicky T. Synlett 2005; 2911
• 25 Schindele C, Houk KN, Mayr H. J. Am. Chem. Soc. 2002; 124: 11208
• 26 Prusinowska N, Czapik A, Kwit M. J. Org. Chem. 2021; 86: 6433