Enantioselective Access to 3-Methylene-1H-indanol through Asymmetric Domino Allylstannylation-Heck Reaction

Abstract

By screening various chiral P,P-ligands in the palladium-catalyzed reaction of ortho-iodobenzaldehyde with allyl tributylstannane, a suitable ligand (Taniaphos) was identified that affords 3-methylene-1-indanol with an enantioselectivity of 96% ee. This result indicates that a ligated palladium intermediate is involved in the chirogenic step of the catalytic cycle (intramolecular electrophilic activation of the aldehyde function by ortho-palladation).

Key words

palladium - enantioselective catalysis - allyl-stannanes - intramolecular - Heck reaction - domino reactions - chiral P,P-ligands

References and Notes

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19

All minima of 9 were optimized with DFT, B3LYP/6-31G(d) using Gaussian 03.^²¹

23

TZVP is a triple-ζ basis set with polarization functions

25

Typical procedure: 2-Iodobenzaldehyde (4a; 116 mg, 0.5 mmol), [Pd₂dba₃] (10.4 mg, 10 µmol, 2 mol%) and ligand L15 (Taniaphos, 15 µmol, 3 mol%) were dissolved in anhydrous DMF (5 mL) under an argon atmosphere. Allyl tributylstannane (0.31 mL, 1.0 mmol, 2 equiv) was added and the resulting mixture was stirred at 80 ˚C for 15 h. After cooling to r.t. sat. aq KF (15 mL) was added and the mixture was extracted with methyl tert-butyl ether (3 × 20 mL). The combined organic layers were washed with brine (20 mL), dried over MgSO₄ and solvents were evaporated. The residue was purified by flash chromatography (SiO₂-KF, 9:1; eluting with cyclohexane-EtOAc, 4:1) to give 9 (38 mg, 52%) as a white-yellowish solid. The enantiomeric purity was determined as 96% ee by means of chiral HPLC (Machery-Nagel Nucleocel Delta S; n-hex-i-PrOH, 99:1; 0.5 mL/min); R _f  = 0.38 (Cyhex-EtOAc, 3:1); mp 71-72 ˚C; [α]_D ^²0 -9.1 (c 1.03, CDCl₃); ^¹H NMR: (300 MHz, CDCl₃):
δ = 2.42 (d, ^³ J = 7 Hz, 1 H, OH), 2.61 (tdd, ⁴ J = 2.5 Hz, ^³ J = 4 Hz, ^² J = 17 Hz, 1 H, H2_A), 3.14 (tdd, ⁴ J = 2 Hz, ^³ J = 7 Hz, ^² J = 17 Hz, 1 H, H2_B), 5.07 (t, ⁴ J = 2 Hz, 1 H, H8_A), 5.20 (dt, ^³ J = 7 Hz, ^³ J = 4 Hz, 1 H, H1), 5.50 (t, ⁴ J = 2.5 Hz, 1 H, H8_B), 7.26-7.34, 7.39-7.45, 7.46-7.53 (3 × m, 4 × 1 H, H4, H5, H6, H7); ^¹³C NMR (75 MHz, CDCl₃): δ = 42.4 (t, C2), 73.2 (d, C1), 104.2 (t, C8), 120.5, 125.0, 128.6, 128.7 (4 × d, C4, C5, C6, C7), 140.1 (s, C3), 146.3, 146.9 (2 × s, C3_a, C7_a); IR (ATR): 3305 (br, m), 3233 (br, m), 3060 (w), 2921 (w), 2733 (w), 1641 (m), 1471 (m), 1423 (m), 1333 (s), 1044 (s), 873 (s), 756 (s), 730 (s) cm^-¹; GC-MS (Optima 1 MS, 10 psi, 50→300 ˚C): t _R = 6.51 min; MS (EI, 70 eV): m/z (%) = 146 (42)[M]⁺, 145 (26), 131 (52), 128 (52), 117 (24), 103 (13), 91 (12), 77 (18), 63 (26), 39 (100); HRMS: m/z calcd for C₁₀H₁₀O: 146.073; found: 146.073 (±0.002).