Synthesis of Spirocyclic Diindeno[1,2-b:2′,1′-d]thiophenes

Abstract

Spirocyclic diindenothiophenes were prepared by cyclization of tosylhydrazones, readily available from ketones, with 3,4-dibromo-2,5-bis(2-bromphenyl)thiophene. For bicyclic ketones, the bis-spirocycles were formed with very good diastereoselectivity.

Key words

catalysis - cyclizations - heterocycles - hydrazones - palladium - spiro compounds

Publication History

Received: 27 June 2022

Accepted after revision: 25 July 2022

Article published online:
26 August 2022

• References and Notes

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• 11 General Procedure for the Synthesis of Spirocycles 4a–gA dioxane solution (5 mL) of 2 (0.27 mmol), 3a (1.08 mmol, 4 equiv.), Pd₂dba₃ (2 mol%), XPhos (4 mol%), and Li ^t BuO (8 equiv.) was stirred for 48 h at 100 °C. To the mixture was added water, and the mixture was extracted three times with dichloromethane. The combined organic layers were dried (MgSO₄), filtered, and concentrated in vacuo. The residue was purified by chromatography (silica gel, EtOAc/heptanes).
• 12 5,5′′-Dichlordispiro{indene-1,10′-diindene[1,2-b:2′,1′-d]thiophene-11′,1′′-indene} (4e)Product 4e was prepared from 2 (150 mg, 0.27 mmol) and 3e (361 mg, 1.08 mmol) as a beige solid (73 mg, 51%); mp 110–114 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.41–7.33 (m, 2 H, H_Ar), 7.16 (td, ³ J = 7.5 Hz, ³ J = 7.5 Hz, ⁴ J = 1.0 Hz, 2 H, H_Ar), 6.95–6.92 (m, 2 H, H_Ar), 6.88 (td, ³ J = 7.5 Hz, ³ J = 7.5 Hz, ⁴ J = 1.1 Hz, 2 H, H_Ar), 6.61 (d, ³ J = 5.4 Hz, 2 H, 2 H_C=C), 6.55–6.49 (m, 4 H, H_Ar), 6.11 (d, ³ J = 8.0 Hz, 2 H, H_Ar), 5.90 (d, ³ J = 5.4 Hz, 2 H, 2 H_C=C) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 146.9, 146.6, 145.8, 142.4, 142.3 (C_Ar/Het), 139.3 (CH_Ar/CH=CH), 139.2, 133.3 (C_Ar/Het), 132.7, 128.1, 126.0, 125.6, 123.0, 122.8, 121.2, 118.7 (CH_Ar/CH=CH), 64.9 (C) ppm. IR (ATR): ν = 3056 (w), 2920 (w), 1599 (w), 1453 (w), 1414 (w), 1282 (w), 1183 (w), 1080 (w), 966 (w), 892 (w), 804 (w), 754 (m), 721 (w), 441 (w) cm^–1. MS (EI, 70 eV): m/z (%) = 530 ([M]⁺, C₃₄H₁₈ ³⁷Cl³⁵ClS, 42), 528 ([M]⁺, C₃₄H₁₈ ³⁵Cl₂S, 55), 494 (33), 493 (71), 458 (67), 457 (49), 456 (92), 281 (100), 253 (77), 251 (43), 229 (63), 227 (36), 210 (30), 208 (56), 207 (51), 195 (37), 193 (71), 192 (31), 191 (32), 179 (43), 51 (35). HRMS (EI): m/z calcd for C₃₄H₁₈ ³⁵Cl₂S [M]⁺: 528.05008; found: 528.04322; m/z calcd for C₃₄H₁₈ ³⁵Cl³⁷ClS [M]⁺: 530.04713; found: 530.04103
• 13 CCDC-2191788 contains supplementary crystallographic data. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures