Two chiral diphosphites, (S,S)-5,17-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-25,26,27,28-tetrapropyloxycalix[4]arene (1) and (S,S)-5,11-bis(1,1′-binaphthyl-2,2′-dioxyphosphanyloxy)-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (2), each based on a conical cavity, were synthesised and assessed in the rhodium-catalysed hydroformylation of vinyl arenes. Under optimised conditions, both ligands led to high proportions of branched aldehyde (b/l = 8.1) in the hydroformylation of styrene. The observed enantioselectivity was considerably higher for 1 than 2 (ee 89% vs. 50%), this being consistent with the easy formation of chelated intermediates with 1 (chelate formation is prevented with 2), in which the embracing ligand enables an efficient chirality transfer to the catalytic centre.

两个手性二亚磷酸酯（（S，S）-5,17-双（1,1'-联萘基-2,2'-二氧代膦酰氧基）-25,26,27,28-四丙氧基杯[4]芳烃（1）和（S，S）-5,11-双（1,1'-联萘基-2,2'-二氧基膦酰氧基）-4（24），6（10），12（16），18（22）-四亚甲基二氧基-2,8分别合成，评估了分别在锥形腔中的1,2,14,20-四戊基间苯二酚[4]芳烃（2），并在铑催化的乙烯基芳烃加氢甲酰化反应中进行了评估。在最佳条件下，两种配体在苯乙烯的加氢甲酰化反应中均导致高比例的支链醛（b / l = 8.1）。1比2观察到的对映选择性高得多（ee 89％vs. 50％），这与容易形成1的螯合中间体（用2阻止了螯合物的形成）相一致，其中包容的配体能够将手性有效转移到催化中心。