(1R,2S,2'S,6S,9a'S)-6-(benzyloxymethyl)-2-hydroxy-2'-((triisopropylsilyloxy)methyl)-6',7',8',9a'-tetrahydro-2'H-spiro[cyclohex[3]ene-1,9'-pyrido[2,1-b][1,3]oxazin]-4'(3'H)-one | 954148-50-6

• 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: (1R,2S,2'S,6S,9a'S)-6-(benzyloxymethyl)-2-hydroxy-2'-((triisopropylsilyloxy)methyl)-6',7',8',9a'-tetrahydro-2'H-spiro[cyclohex[3]ene-1,9'-pyrido[2,1-b][1,3]oxazin]-4'(3'H)-one
• 英文别名: (2S,3'S,5'S,9S,9aS)-3'-hydroxy-5'-(phenylmethoxymethyl)-2-[tri(propan-2-yl)silyloxymethyl]spiro[2,3,6,7,8,9a-hexahydropyrido[2,1-b][1,3]oxazine-9,4'-cyclohexene]-4-one
• CAS: 954148-50-6
• 化学式: C₃₁H₄₉NO₅Si
• 分子量: 543.819
• InChiKey: CJIMGLNAESQNEK-JBUMCTQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.06
• 重原子数：
  38
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  68.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2S,2'S,6S,9a'S)-6-(benzyloxymethyl)-2-hydroxy-2'-((triisopropylsilyloxy)methyl)-6',7',8',9a'-tetrahydro-2'H-spiro[cyclohex[3]ene-1,9'-pyrido[2,1-b][1,3]oxazin]-4'(3'H)-one 在 manganese(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以91%的产率得到(1R,2'S,6S,9a'S)-6-(benzyloxymethyl)-2'-((triisopropylsilyloxy)methyl)-6',7',8',9a'-tetrahydro-2'H-spiro[cyclohex[3]ene-1,9'-pyrido[2,1-b][1,3]oxazin]-2,4'(3'H)-dione
  参考文献：
  名称：

  The First Synthesis of the ABC-Ring System of ‘Upenamide

  摘要：

  The first synthetic route to the spirooxaquinolizidinone core (ABC core) of the macrocyclic marine alkaloid 'upenamide (1) has been developed. All five stereocenters were introduced with complete stereocontrol. The hydroxyl group at C-11 was introduced by a regio- and stereoselective SeO2-mediated allylic oxidation. The spirocyclic skeleton was formed by a stannous chloride induced deacetalization-bicyclization procedure. Further stereocenters were introduced by an enzymatic desymmetrization and by incorporation of an (S)-malic acid derived building block.

  DOI：

  10.1021/ol701772d
• 作为产物：
  描述：

  ((1R,6S)-6-(hydroxymethyl)cyclohex-3-en-1-yl)methyl acetate 在 2,6-二甲基吡啶 、 lithium hydroxide 、 selenium(IV) oxide 、 jones' reagent 、 4 A molecular sieve 、 二苯基膦叠氮化物 、 四丁基氟化铵 、 水 、 magnesium oxide 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 N,N-二异丙基乙胺 、 乙酰氯 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 tin(ll) chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 67.75h， 生成 (1R,2S,2'S,6S,9a'S)-6-(benzyloxymethyl)-2-hydroxy-2'-((triisopropylsilyloxy)methyl)-6',7',8',9a'-tetrahydro-2'H-spiro[cyclohex[3]ene-1,9'-pyrido[2,1-b][1,3]oxazin]-4'(3'H)-one
  参考文献：
  名称：

  The First Synthesis of the ABC-Ring System of ‘Upenamide

  摘要：

  The first synthetic route to the spirooxaquinolizidinone core (ABC core) of the macrocyclic marine alkaloid 'upenamide (1) has been developed. All five stereocenters were introduced with complete stereocontrol. The hydroxyl group at C-11 was introduced by a regio- and stereoselective SeO2-mediated allylic oxidation. The spirocyclic skeleton was formed by a stannous chloride induced deacetalization-bicyclization procedure. Further stereocenters were introduced by an enzymatic desymmetrization and by incorporation of an (S)-malic acid derived building block.

  DOI：

  10.1021/ol701772d

文献信息

• The First Synthesis of the ABC-Ring System of ‘Upenamide
  作者：Jan Peter Schmidt、Sandra Beltrán-Rodil、Rhona J. Cox、Graeme D. McAllister、Mark Reid、Richard J. K. Taylor

  DOI：10.1021/ol701772d

  日期：2007.9.1

  The first synthetic route to the spirooxaquinolizidinone core (ABC core) of the macrocyclic marine alkaloid 'upenamide (1) has been developed. All five stereocenters were introduced with complete stereocontrol. The hydroxyl group at C-11 was introduced by a regio- and stereoselective SeO2-mediated allylic oxidation. The spirocyclic skeleton was formed by a stannous chloride induced deacetalization-bicyclization procedure. Further stereocenters were introduced by an enzymatic desymmetrization and by incorporation of an (S)-malic acid derived building block.