Pnictogen-bond donors are attractive for use in catalysis because of deep σ holes, high multivalency, rich hypervalency, and chiral binding pockets. We here report natural product inspired epoxide-opening polyether cyclizations catalyzed by fluoroarylated Sb(V) > Sb(III) > Bi > Sn > Ge. The distinctive characteristic found for pnictogen-bonding catalysis is the breaking of the Baldwin rules, that is selective endo cyclization into the trans-fused ladder oligomers known from the brevetoxins. Moreover, tris(3,4,5-trifluorophenyl)stibines and their hypervalent stiborane catecholates afford different anti-Baldwin stereoselectivity. Lewis (SbCl₃), Brønsted (AcOH) and π acids fail to provide similar access to these forbidden rings. Like hydrogen-bonding catalysis differs from Brønsted acid catalysis, pnictogen-bonding catalysis thus emerges as the supramolecular counterpart of covalent Lewis acid catalysis.

中文翻译：

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光子键催化：短毒素型聚醚环化

光子键供体由于具有较大的σ孔，高多价，丰富的高价和手性结合口袋，因此在催化中具有吸引力。我们在此报告了由氟代芳基化的Sb（V）> Sb（III）> Bi> Sn> Ge催化的天然产物启发的开环聚醚环化反应。为氮族元素接合催化的独特特性发现的是的鲍德温规则的断裂，即选择性内切环化到反式从brevetoxins已知-融合梯低聚物。此外，三（3,4,5-三氟苯基）stibines及其高价stiborane儿茶酚酯具有不同的抗-Baldwin立体选择性。刘易斯（SbCl ₃），布朗斯台德（AcOH）和π酸无法为这些禁环提供类似的通道。就像氢键催化不同于布朗斯台德酸催化一样，光子键催化也因此作为共价路易斯酸催化的超分子形式出现。