Oxa-di-π-methane Rearrangement of a Substrate Embodying the Platencin Core Provides the Decahydro-1H-cyclopenta[c]indene Framework Associated with Various Diterpenes and Certain Lycopodium Alkaloids

Abstract

A chemoenzymatic approach to the title framework is reported. The reaction sequence starts with the whole-cell biotransformation of iodobenzene and the conversion of the resulting homochiral metabolite into a triene that engages in an intramolecular Diels–Alder reaction and so affording an adduct embodying the platencin core. Application of an oxa-di-π-methane rearrangement to a derivative of this core affords a cyclopropannulated form of the target framework; the latter is then obtained through a TMSI-mediated cleavage of the three-membered ring. A strategy for the assembly of the enantiomeric framework is also described.

Key words

cyclopentaindenes - cycloaddition - enzymes - photochemistry - ring-opening

Publication History

Received: 10 February 2023

Accepted after revision: 20 March 2023

Accepted Manuscript online:
20 March 2023

Article published online:
17 May 2023

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• 28 Representative Spectral Data: Compound 16 IR (ATR): 2932, 2866, 1714, 1456, 1379, 1262, 1249, 1207, 1089, 1069, 722 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 6.24 (m, 1 H), 5.99 (d, J = 8.4 Hz, 1 H), 4.36 (d, J = 7.3 Hz, 1 H), 4.13 (m, 1 H), 2.82 (s, 1 H), 2.63 (m, 1 H), 2.35 (broadened, J = 11.3 Hz, 1 H), 1.98 (m, 1 H), 1.74–1.60 (complex m, 4 H), 1.31–1.21 (complex m, 7 H), 0.90 (m, 1 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 212.4, 131.7, 128.8, 108.7, 78.6, 78.0, 57.4, 40.4, 39.9, 35.1, 31.7, 28.8, 27.5, 25.6, 25.1. MS (ESI, +ve): m/z = 519 [2M + Na]⁺, 100%, 271 [M + Na]⁺, 20. HRMS (TOF ESI, +ve): m/z [M + Na]⁺ calcd for C₁₅H₂₀NaO₃: 271.1310; found: 271.1313. Compound 23 IR (ATR): 2930, 2858, 1741, 1094, 1072, 737, 698 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.37–7.29 (complex m, 5 H), 4.76 (d, J = 11.9 Hz, 1 H), 4.49 (d, J = 11.9 Hz, 1 H), 3.37 (dd, J = 11.5 and 4.6 Hz, 1 H), 2.89 (d, J = 17.9 Hz, 1 H), 2.74 (t, J = 5.7 Hz, 1 H), 2.20 (m, 1 H), 2.07–1.97 (complex m, 2 H), 1.84–1.74 (complex m, 3 H), 1.68–1.63 (complex m, 2 H), 1.51–1.40 (complex m, 3 H), 1.23 (m, 1 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 215.8, 138.7, 128.6, 127.9, 127.8, 78.9, 70.9, 54.6, 54.3, 50.0, 40.8, 34.2, 31.5, 30.3, 28.3, 27.6, 23.6. MS (ESI, +ve): m/z = 305 [M + Na]⁺, 100%. HRMS (TOF ESI, +ve): m/z [M + Na]⁺ calcd for C₁₉H₂₂NaO₂: 305.1517; found: 305.1517. Compound 25 IR (ATR): 2930, 2865, 1741, 1455, 1400, 1166, 1074, 742, 699 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.35–7.27 (complex m, 3 H), 7.25–7.23 (complex m, 2 H), 4.59 (d, J = 11.6 Hz, 1 H), 4.34 (d, J = 11.6 Hz, 1 H), 3.82 (m, 1 H), 3.39–3.31 (complex m, 2 H), 2.69–2.54 (complex m, 2 H), 2.17–2.03 (complex m, 5 H), 1.98 (m, 1 H), 1.87–1.65 (complex m, 3 H), 1.52 (m, 1 H), 1.32 (m, 1 H). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 217.8, 138.1, 128.5, 128.0, 127.8, 83.0, 71.2, 55.6, 53.4, 49.3, 45.9, 44.8, 43.9, 28.7, 27.6, 25.6, 21.7. MS (ESI, +ve): m/z = 433 [M + Na]⁺, 100%. HRMS (TOF ESI, +ve): m/z [M + Na]⁺ calcd for C₁₉H₂₃INaO₂: 433.0640; found: 433.0642.