Synlett 2017; 28(08): 973-975
DOI: 10.1055/s-0036-1589936
letter
© Georg Thieme Verlag Stuttgart · New York

Phosphorus-Substituted Azulenes Accessed via Direct Hafner Reaction of a Phosphino Cyclopentadienide

Anthony P. Gee
Department of Chemistry, University of Bath, , Bath, BA2 7AY, UK   Email: S.E.Lewis@bath.ac.uk
,
Samuel D. Cosham
Department of Chemistry, University of Bath, , Bath, BA2 7AY, UK   Email: S.E.Lewis@bath.ac.uk
,
Andrew L. Johnson
Department of Chemistry, University of Bath, , Bath, BA2 7AY, UK   Email: S.E.Lewis@bath.ac.uk
,
Simon E. Lewis*
Department of Chemistry, University of Bath, , Bath, BA2 7AY, UK   Email: S.E.Lewis@bath.ac.uk
› Author Affiliations
Further Information

Publication History

Received: 08 November 2016

Accepted after revision: 27 December 2016

Publication Date:
17 January 2017 (online)


Abstract

The Hafner azulene synthesis may be applied to the direct synthesis of phosphorus-substituted azulenes, when a phosphinocyclopentadienide is used as one of the reactants. The azulenyl phosphines produced in this fashion are preferentially isolated as the corresponding phosphine oxides or phosphine borane adducts.

Supporting Information

 
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  • 17 Procedure for the Preparation of 8 At 0 °C, to a suspension of 2,4,6-trimethylpyrylium tetrafluoroborate (5, 1.10 g, 5.23 mmol, 1.00 equiv) in THF (30 mL) was added a solution of lithium (diphenylphosphino)cyclopentadienide (4, 2.68 g, 10.5 mmol, 2.00 equiv) in THF (30 mL). After stirring at 0 °C for 1 h, the mixture was filtered through a pad of neutral alumina under an atmosphere of argon. To the stirred filtrate, at r.t., was slowly added a solution of borane–THF complex (11.0 mL, 1.0 M in THF, 2.10 equiv). After stirring for 16 h, the reaction was quenched by the addition of MeOH (10 mL). The solution was then concentrated under reduced pressure to a small volume, and added to EtOAc (60 mL). The solution was washed with water (3 × 50 mL) and with sat. brine, the organic layer was dried over anhydrous MgSO4, and filtered. The filtrate was concentrated under reduced pressure to give the crude product, which was purified by column chromatography (0 → 10% EtOAc in PE) to give boranyldiphenyl(4,6,8-trimethylazulen-2-yl)phosphine (8, 228 mg, 0.621 mmol, 12%) as a purple solid (mp 148–150 °C). Rf = 0.53 (PE–EtOAc, 3:1). 1H NMR (300 MHz, CDCl3): δ = 7.73–7.66 (4 H, m), 7.51–7.41 (6 H, m), 7.46 (2 H, d, 3J PH = 5.1 Hz), 7.12 (2 H, s), 2.83 (6 H, s), 2.65 (3 H, s), 1.44 (3 H, br d); 13C NMR (75 MHz, CDCl3): δ = 149.7, 148.7, 136.5 (d, 3 J CP = 11.5 Hz), 133.0 (d, 2J CP = 9.9 Hz), 131.1 (d, 1 J CP = 62.7 Hz), 130.8 (d, 4 J CP = 2.5 Hz), 130.6 (d, 1 J CP = 58.9 Hz), 128.5 (d, 3 J CP = 10.2 Hz), 128.3 (d, 5 J CP = 1.2 Hz), 120.8 (d, 2 J CP = 10.5 Hz), 29.0, 25.2. 31P NMR (122 MHz, CDCl3): δ = 12.38–11.65 (m). 11B NMR (96 MHz, CDCl3): δ = –34.5. IR (film): νmax = 3675, 2987, 2971, 2901, 2380 (νBH), 1578, 1537, 1483, 1468, 1435, 1408, 1394, 1377, 1333, 1290, 1218, 1187, 1140, 1102, 1027, 1066, 907, 882, 847, 809, 797, 766, 740, 690 cm–1. HRMS (ESI+): m/z calcd for [C25H26BP + Na]+: 391.1763; found: 391.1796. See Supporting Information for complete NMR assignments.
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