A convenient and efficient regioselective synthesis of phosphorylated 3-(β-hydroxy)allenes by an atom economical [2,3]-sigmatropic rearrangement of the mediated propargyl phosphite or phosphinite which can be readily prepared via reaction of protected 5-(tetrahydro-2H-pyran-2-yloxy)-hex-1-yn-3-ol with dimethyl chlorophosphite or chlorodiphenyl phosphine, respectively, is described. This paper discusses a reaction of phosphorylated 3-(β-hydroxy)allenes with protected or unprotected hydroxy group involving 5-endo-trig cyclization or 2,3-addition. Reaction of 3-(β-hydroxy)allenephosphonates with electrophiles that produces 2-oxo-2,5-dihydro-1,2-oxaphospholes due to the participation of the phosphonate neighboring group in the cyclization is described. On the other hand, 5-hydroxyhex-(1E)-enyl phosphine oxides were prepared by chemo-, regio-, and stereoselective electrophilic addition to the C2-C3 double bond in the allenyl phosphine oxides and subsequent attack of the external (chloride anion) nucleophile. Phosphorylated 3-(β-hydroxy)allenes were smoothly converted into the corresponding 2-phosphoryl-5,6-dihydro-2H-pyrans by using 5 mol % of coinage metal salt as catalyst in 6-endo-trig cycloisomerization reaction.

中文翻译：

---

双功能化丙二烯，第 XIX 部分：磷酸化 3-（β-羟基）丙二烯的合成、亲电环化/加成和造币金属催化的环异构化

通过介导的炔丙基亚磷酸酯或亚膦酸酯的原子经济 [2,3]-σ 重排，方便有效地区域选择性合成磷酸化 3-（β-羟基）丙二烯，可通过受保护的 5-（四氢-2H）反应轻松制备-pyran-2-yloxy)-hex-1-yn-3-ol 分别与二甲基氯亚磷酸酯或氯二苯基膦进行描述。本文讨论了磷酸化 3-（β-羟基）丙二烯与受保护或未受保护的羟基的反应，涉及 5-endo-trig 环化或 2,3-加成。描述了 3-(β-羟基) 丙二烯膦酸酯与亲电子试剂的反应，由于膦酸酯相邻基团参与环化反应，产生 2-oxo-2,5-dihydro-1,2-oxaphospholes。另一方面，5-羟基己-(1E)-烯基氧化膦通过化学-、区域-、和立体选择性亲电加成到丙二烯基氧化膦中的 C2-C3 双键，随后攻击外部（氯阴离子）亲核试剂。在6-endo-trig环异构化反应中，使用5 mol %的铸币金属盐作为催化剂，将磷酸化的3-(β-羟基)丙二烯顺利地转化为相应的2-磷酰基-5,6-二氢-2H-吡喃。