近期化學家開發之有機連鎖合成策略，在合成多個掌性中心的產物分子反應，開展有機合成新的領域，特別是在天然物的全合成，以及藥物化學。有機不對稱催化連鎖反應，為一種低成本高效率的合成方式，避免繁瑣分離及純化中間產物的操作，減少保護以及去保護基的步驟，降低時間和成本的消耗；另一方面，此種反應類型可同時建立多個碳-碳鍵以及立體化學中心，合成出具有高鏡像選擇性的化合物。本實驗發展出以硫尿素雙氫鍵衍生之有機催化劑與鹼性試劑共催化的方式，促使硝基烯類與乙醛酸乙酯進行Morita-Baylis-Hillman反應，製備硝基烯丙醇化合物。以20 mol%的4-二甲氨基吡啶，在無溶劑的條件，室溫下與20 mol%的硫尿素雙氫鍵衍生之有機催化劑進行共催化，或是將鹼性添加劑改成咪唑（100 mol%），可在水溶液中進行反應。此兩種方法，皆可在短時間內得到高產率（56-92%）的2-羥基-3-硝基-4-芳香環類/烷類-3-丁烯酸酯衍生物。更進一步地，以2-芳香環亞甲基氫茚-1,3-二酮與醛類為前驅物，成功合成出多取代二螺環己烷衍生之預期產物。此三分子的有機不對稱催化連鎖反應，在,-L-雙苯環脯胺醇矽醚有機催化劑（5 mol%）的催化下，以二甲基甲醯胺為溶劑，1,4-二氮雜二環[2.2.2]辛烷（20 mol%）為添加劑，反應溫度為-20 oC的最佳條件下進行。其反應機構是經由兩次的Michael加成反應，接著進行分子內aldol環化反應，可得到不錯的產率以及>95:5的非鏡像選擇性，鏡像超越值高達99% ee。

Newly developed organocascade strategies have emerged as promising protocols for the synthesis of complex organic molecules with multiple stereogenic centers. In particular, asymmetric organocatalyzed multi-component “domino” reactions, used during total syntheses of natural products and continued to be important in biology and pharmacology. Domino reactions avoid time-consuming and costly protection/deprotection steps. It is especially appealing owing to such decisive synthetic advantages as synthetic efficiency, atom economy, operational simplicity, and the minimal need for the isolation and purification process. On the other hand, these reactions which involving two or more bond-forming reactions under identical reaction conditions often provide specific targeted molecules with excellent stereoselectivities. Here we report an efficient thiourea promoted MBH reaction of various conjugated nitroalkenes with ethyl glyoxylate. The desired multifunctional products, 2-hydroxy-3-nitro-4-aryl/alkylbut-3-enoate derivatives were obtained in good to high chemical yields (56-92%) with DMAP (20 mol%) under solvent-free conditions or imidazole (100 mol%) in the presence of water. Furthermore, an interesting organocatalytic reaction between 2-arylideneindane-1,3-diones and aldehydes has been developed that gives fully substituted and highly strained dispirocyclohexane derivatives. This three-component domino reaction proceeds by way of a catalyzed Michael/Michael/aldol cyclization sequence affording the products with reasonable-to-good chemical yields and with high stereoselectivities (>95:5 d.r. and up to 99% ee) using a catalytic amount of commercially available ,-L-diphenylprolinol trimethylsilyl ether (5 mol%) and DABCO (20 mol%) in DMF at -20 oC.

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