<div><p></p><p>New chiral ferrocenylphosphines <b>LB1</b>–<b>LB9</b> were designed and prepared through simple synthetic approaches. These air-stable ferrocenylphosphines were applied to promote asymmetric [3+2]-cycloaddition of Morita–Baylis–Hillman carbonates with maleimides, among which <b>LB7</b> was shown to have good catalytic activity to afford the corresponding multifunctional cyclopentenes in up to 59% yield and up to 53% <i>ee</i> under mild reaction conditions. A plausible reaction mechanism was proposed.</p>
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