(+/-)-17,18-Didehydro-20,23-bis(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane | 138458-91-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂螺癸烷衍生物
• 英文名称: (+/-)-17,18-Didehydro-20,23-bis(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane
• CAS: 138458-91-0
• 化学式: C₃₆H₄₇NO₂
• 分子量: 525.775
• InChiKey: FZJWIMKZRLGVKS-DXUFPPSBSA-N

反应信息

• 作为反应物：
  描述：

  (+/-)-17,18-Didehydro-20,23-bis(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane 在 palladium(II) trifluoroacetate 、 三苯基膦 、 对苯醌 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以70%的产率得到(1α,3aβ,5aβ,6α,8aα,11aβ,11bβ,11cβ,12R^*)-(+/-)-Tetradecahydro-3-methylene-5a-<(phenylmethoxy)methyl>-11b-<3-(phenylmethoxy)propyl>-1,6,8a-metheno-2H-azuleno<5,4-g>indole
  参考文献：
  名称：

  Daphniphyllum alkaloids. 14. Total synthesis of (.+-.)-bukittinggine

  摘要：

  The unique heptacyclic Daphniphyllum alkaloid bukittinggine (1) has been prepared by total synthesis. The basic secodaphnane nucleus was fashioned in one step by application of the tetracyclization process to dihydroxy diether 5. The pyrrolidine ring in 1 was formed by a Pd(II)-catalyzed oxidative cyclization of 19 to give hexacyclic amine 32. Hydrogenation of 32 proceeded with little diastereoselectivity in establishing the final stereocenter in 1. However, when 32 was treated to the sequence of hydroboration/oxidation, tosylation, and reduction, excellent control of stereochemistry was observed in the formation of 33. Debenzylation of 33 (Na-liquid NH3), followed by regiospecific oxidative lactonization of diol 36 (Fetizon's reagent), afforded (+/-)-bukittinggine (1). The synthesis required 18 steps (9 --> 10 --> 11 --> 12 --> 13 --> 14 --> 15 --> 8 --> 16 --> 17 --> 18 --> 5 --> 19 --> 32 --> 35 --> 33 --> 36 --> 1) and delivered racemic bukittinggine in 3% overall yield.

  DOI：

  10.1021/jo00035a011
• 作为产物：
  描述：

  (4aR,7aS)-7a-((Z)-4-Benzyloxymethyl-8-methyl-nona-3,7-dienyl)-4-(3-benzyloxy-propyl)-5,6,7,7a-tetrahydro-4aH-[2]pyrindine 在 ammonium acetate 、 溶剂黄146 作用下， 生成 (+/-)-17,18-Didehydro-20,23-bis(phenylmethoxy)-12,16-cyclo-1,12-secodaphnane
  参考文献：
  名称：

  Daphniphyllum alkaloids. 14. Total synthesis of (.+-.)-bukittinggine

  摘要：

  The unique heptacyclic Daphniphyllum alkaloid bukittinggine (1) has been prepared by total synthesis. The basic secodaphnane nucleus was fashioned in one step by application of the tetracyclization process to dihydroxy diether 5. The pyrrolidine ring in 1 was formed by a Pd(II)-catalyzed oxidative cyclization of 19 to give hexacyclic amine 32. Hydrogenation of 32 proceeded with little diastereoselectivity in establishing the final stereocenter in 1. However, when 32 was treated to the sequence of hydroboration/oxidation, tosylation, and reduction, excellent control of stereochemistry was observed in the formation of 33. Debenzylation of 33 (Na-liquid NH3), followed by regiospecific oxidative lactonization of diol 36 (Fetizon's reagent), afforded (+/-)-bukittinggine (1). The synthesis required 18 steps (9 --> 10 --> 11 --> 12 --> 13 --> 14 --> 15 --> 8 --> 16 --> 17 --> 18 --> 5 --> 19 --> 32 --> 35 --> 33 --> 36 --> 1) and delivered racemic bukittinggine in 3% overall yield.

  DOI：

  10.1021/jo00035a011