(1S,7aS)-1-(tosyloxy)-7a-methyl-7,7a-dihydro-5(6H)-indanone | 144299-24-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,7aS)-1-(tosyloxy)-7a-methyl-7,7a-dihydro-5(6H)-indanone
• 英文别名: [(1S,7aS)-7a-methyl-5-oxo-2,3,6,7-tetrahydro-1H-inden-1-yl] 4-methylbenzenesulfonate
• CAS: 144299-24-1
• 化学式: C₁₇H₂₀O₄S
• 分子量: 320.409
• InChiKey: YWPXUQJGLVSIJA-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,7aS)-1-(tosyloxy)-7a-methyl-7,7a-dihydro-5(6H)-indanone 在 盐酸 、 sodium tetrahydroborate 、 二异丁基氢化铝 、 对甲苯磺酸 作用下， 以 乙醇 、 二甲基亚砜 、 丙酮 、 甲苯 、 苯 为溶剂， 反应 12.5h， 生成 (7aR)-1-hydroxymethyl-7a-methyl-2,3,5,6,7,7a-hexahydro-1H-inden-5-one
  参考文献：
  名称：

  旨在通过阴离子多环化反应合成不对称的心脏活性类固醇的研究。

  摘要：

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。

  DOI：

  10.1021/ol027125o
• 作为产物：
  描述：

  (S)-(+)-2,3,7,7A-四氢-7A-甲基-1H-茚-1,5(6H)-二酮 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 4.0h， 生成 (1S,7aS)-1-(tosyloxy)-7a-methyl-7,7a-dihydro-5(6H)-indanone
  参考文献：
  名称：

  旨在通过阴离子多环化反应合成不对称的心脏活性类固醇的研究。

  摘要：

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。

  DOI：

  10.1021/ol027125o

文献信息

• Studies towards the Synthesis of (+)‐Dictyoxetane
  作者：Joseph Benford‐Ward、Sanaz Ahmadipour、Aliya Sembayeva、Louise Male、Richard S. Grainger

  DOI：10.1002/chem.202202429

  日期：2022.12.20

  Hajos-Parrish ketone is used to prepare a key building block for the total synthesis of the marine natural product dictyoxetane in enantiopure form. A synthetic alternative to the Garst-Spencer furan annelation is developed, and the reactivity and diastereoselectivity of the resulting tetrasubstituted chiral furan in cycloaddition reactions towards an appropriately functionalised carbocyclic core of dictyoxetane

  Hajos-Parrish 酮用于制备对映体纯形式的海洋天然产物双氧环乙烷全合成的关键构件。开发了 Garst-Spencer 呋喃环化的合成替代品，并探索了所得四取代手性呋喃在环加成反应中对双氧杂环丁烷的适当官能化碳环核的反应性和非对映选择性。
• Synthesis and photochemical rearrangement of (1(R),7a(S))-1-(tert-butyldiphenylsiloxy)-7a-methyl-5(7aH)-indanone
  作者：Drury Caine、Pravin L. Kotian

  DOI：10.1021/jo00050a040

  日期：1992.11

  Reaction of (1S,7aS)-1-hydroxy-7a-methyl-7,7a-dihydro-5(6H)-indanone (5a) with benzoic acid under the usual conditions of the Mitsunobu reaction gave a low yield of a 1:1 mixture of the benzoate derivatives 6b and 5b resulting from inversion and retention of configuration, respectively, at C-1. Under conditions in which the benzoic acid concentration was kept low, only the inversion product 6b was obtained but the extent of conversion of the alcohol to the ester was low. The substitution of p-nitrobenzoic acid for benzoic led to a significant improvement in the yield of the inversion product 6c. Several other methods of obtaining alpha-oxy derivatives of the type 6b-e were explored but with little or no success. The reaction of the tosyloxy enone 5d with azide ion and cyanide anion gave enones of the type 12 resulting from retention of configuration at C-1 largely or exclusively. The (p-nitrobenzoyl)oxy derivative 6c was converted into the corresponding cross-conjugated cyclohexadienone, (1R,7aS)-l-(tert-butyldiphenylsiloxy)-7a-methyl-5(7aH)-indanone (4a), which was irradiated in glacial and in aqueous acetic acid. In the former solvent, the dienone system underwent photochemical rearrangement to give the 5/6-fused acetoxyl enone 14 and a 2:1 mixture of the tricyclic cyclopropyl ketone 15 and 16 in 25% and 17% yields, respectively, but in aqueous acetic acid phenolic products 18 and 20, obtained by thermal cleavage of the 1,7a carbon-carbon bond, were obtained almost exclusively. In contrast, under the same photolysis conditions, the dienone 1a, the C-1beta epimer of 4a, gave a mixture of photoproducts composed of the 5/6-fused hydroxy ketone 21, the 5/6-fused acetoxy ketone 2a, and the tricyclic conjugated cyclopropyl ketone 22 in 47%, 5%, and 15% yields, respectively.
• Studies Directed toward Asymmetric Synthesis of Cardioactive Steroids via Anionic Polycyclization
  作者：Zhixiang Yang、Dean Shannon、Vouy-Linh Truong、Pierre Deslongchamps

  DOI：10.1021/ol027125o

  日期：2002.12.1

  [reaction: see text] The use of anionic polycyclization (AP) in constructing the steroidal backbone of cardenolides was investigated. The reaction of 2-carbomethoxy-2-cyclohexenone I with the enolate of Nazarov reagent II gave, after decarboxylation and aldol condensation, steroid III with control of stereochemistry.

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。