Ligand Tailoring: The First Modular Assembly of Atropisomeric Biarylbisphosphine Ligands

Abstract

Strategies based on highly selective halogen-metal permutations have been devised and applied enabling the modular assembly of atropisomeric biaryl bisphosphines. After resolution on chiral column, the ligands were tested in benchmark hydrogenation reactions affording good to excellent enantioselectivity.

Key words

lithiation - phosphorus - catalysts - hydrogenation - bi­aryls

References and Notes

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28

Representative Procedure for the Selective Bromine-Lithium Exchange.
n-BuLi (0.10 mol) in hexanes (63 mL) was added at -75 °C to a solution of 2,2′,6,6′-tetrabromo-1,1′-biphenyl (47 g, 0.10 mol) in THF (500 mL). The mixture was consecutively treated with fluorodimethoxyborane diethyl ether (19 mL, 16 g, 0.10 mol), a 3.0 M aq solution of NaOH (36 mL) and 30% aq H₂O₂ (10 mL, 3.6 g, 0.10 mol). The reaction mixture was neutralized at 25 °C with 2.0 M HCl (100 mL) and extracted with Et₂O (3 × 100 mL). The combined organic layers were washed with a 10% aq solution of Na₂SO₃ (100 mL), dried over Na₂SO₄ and evaporated. The oily residue was dissolved in DMSO (200 mL) before MeI (7.5 mL, 17 g, 0.12 mol) and KOH powder (6.7 g, 0.12 mol) were consecutively added. After 1 h, H₂O (500 mL) was added and the product was extracted with Et₂O (3 × 100 mL). The organic layers were dried over Na₂SO₄ and evaporated. Crystallization from EtOH (100 mL) afforded 35 g (82%) product as colorless cubes; mp 184-185 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.64 (d, J = 8.3 Hz, 2 H), 7.30 (m, 2 H), 7.11 (t, J = 8.1 Hz, 1 H), 6.96 (dd, J = 7.2, 2.2 Hz, 1 H), 3.77 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 157.6, 139.5, 131.5, 130.5, 130.2, 125.1, 124.6, 124.3, 110.0, 56.3. Anal. Calcd (%) for C₁₃H₉Br₃O (420.92): C, 37.09; H, 2.16. Found: C, 37.10; H 2.03.