2-<3,4-(Methylenedioxy)phenyl>-1-cyclopentanone | 163813-73-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 2-<3,4-(Methylenedioxy)phenyl>-1-cyclopentanone
• 英文别名: 2-(benzo[d][1,3]dioxol-5-yl)cyclopentanone；2-(Benzo[d][1,3]dioxol-5-yl)cyclopentan-1-one；2-(1,3-benzodioxol-5-yl)cyclopentan-1-one
• CAS: 163813-73-8
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: WHJSAMFAHNUQPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-<3,4-(Methylenedioxy)phenyl>-1-cyclopentanone 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成 6-Benzo[1,3]dioxol-5-yl-tetrahydro-pyran-2-one
  参考文献：
  名称：

  Photoinduced Molecular Transformations. 157. A New Stereo- and Regioselective Synthesis of 2,6-Diaryl-3,7-dioxabicyclo[3.3.0]octane Lignans Involving a .beta.-Scission of Alkoxyl Radicals as the Key Step. New Total Syntheses of (.+-.)-Sesamin, (.+-.)-Eudesmin, and (.+-.)-Yangambin

  摘要：

  New total syntheses of naturally occurring 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans, (+/-)-sesamin and (+/-)-eudesmin, and the first total synthesis of (+/-)-yangambin were achieved according to a general method devised by Suginome and colleagues for replacing the carbonyl group of the cyclopentanone ring with an oxygen atom to give a corresponding tetrahydrofuran ring involving a regioselective beta-scission of alkoxyl radicals; arylation of dimethyl, diallyl, or dibenzyl 3,7-dioxobicyclo[3.3.0]octane-2,6-dicarbonate (18 and 19a,b) with aryllead triacetate 9a-c, followed by dealkoxycarbonylation of the resulting arylated product 20a-f, gave 2,6-diaryl-3,7-dioxobicyclo-[3.3.0]octane 21a-c. A regioselective Baeyer-Villiger oxidation of 21a-e with m-CPBA-NaHCO3 or -K2CO3 gave the corresponding delta-lactone 22a-c, which was reduced with DIBAL to give the corresponding lactol 23a-c. The irradiation of a solution of the hypoiodite of 23a-c, generated in situ with mercury(II) oxide-iodine, in benzene with Pyrex-filtered light resulted in a regioselective beta-scission of the corresponding alkoxyl radical to give iodo formate 24a-c. Heating 24a-c in MeOH with NaBH4 gave (+/-)-sesamin (25a), (+/-)-eudesmin (25b), or (+/-)-yangambin (25c).

  DOI：

  10.1021/jo00115a021
• 作为产物：
  描述：

  2-氧代环戊羧酸烯丙酯 在 吡啶 、 甲酸 、 palladium diacetate 、 1,2-双(二苯基膦)乙烷 作用下， 以 1,4-二氧六环 、 氯仿 为溶剂， 反应 28.0h， 生成 2-<3,4-(Methylenedioxy)phenyl>-1-cyclopentanone
  参考文献：
  名称：

  受阻位叔α-芳基酮的催化不对称合成

  摘要：

  一系列叔α-芳基环戊酮和环己酮的催化不对称合成是通过相应的α-芳基-β-酮烯丙基烯丙基酯的Pd催化脱羧质子化而完成的。对映选择性高达92％ee和74％ee分别对环戊酮和环己酮底物进行了测定。所描述的途径允许以中等至高水平的对映选择性进入这些重要的结构基序。特别地，这仅仅是制备叔α-芳基环戊烷酮的第二种直接方法。合成方法允许对芳基进行简单的修饰。重要的是，含有空间位阻芳基的底物具有最高水平的对映选择性，并且这些芳基易于通过Pb介导的β-酮烯丙基酯的芳基化反应而安装。

  DOI：

  10.1021/jo5014806

文献信息

• Photoinduced C-C Bond Cleavage and Oxidation of Cycloketoxime Esters
  作者：Binlin Zhao、Hui Tan、Cheng Chen、Ning Jiao、Zhuangzhi Shi

  DOI：10.1002/cjoc.201800206

  日期：2018.11

  the traditional Beckmann rearrangement process has been established to build cyano‐containing ketones in the presence of photocatalyst. This novel transformation is remarkable with selective C—C bond cleavage and an oxidation process enabled by DMSO used as the solvent, oxidant, and oxygen source avoiding acid, base and toxic cyanide salts as the cyano source. Further applications in late‐stage modification

  已经建立了超越传统贝克曼重排过程的环酮肟酯的新型结构重组，以在光催化剂存在下构建含氰基的酮。这种新颖的转化过程具有显着的选择性CC键断裂和DMSO作为溶剂，氧化剂和氧源而避免了酸，碱和有毒氰化物盐作为氰基源的氧化过程。也已经报道了在复杂和手性分子的后期修饰中的进一步应用。
• Enantioselective Radical Ring-Opening Cyanation of Oxime Esters by Dual Photoredox and Copper Catalysis
  作者：Jun Chen、Peng-Zi Wang、Bin Lu、Dong Liang、Xiao-Ye Yu、Wen-Jing Xiao、Jia-Rong Chen

  DOI：10.1021/acs.orglett.9b03970

  日期：2019.12.6

  Catalytic enantioselective chemical reactions involving highly reactive radical species remain largely unexplored. We report herein for the first time a novel enantioselective radical ring-opening cyanation of redox-active oxime esters by dual photoreodox and copper catalysis. This mild protocol shows good functional group tolerance and broad substrate scope, producing a wide range of optically active

  涉及高反应性自由基种类的催化对映选择性化学反应在很大程度上仍未开发。我们在此首次报道了通过双重光致氧化和铜催化的氧化还原活性肟酯的新型对映选择性自由基开环氰化反应。这种温和的方案显示出良好的官能团耐受性和广泛的底物范围，可生产出高收率和出色的对映选择性的多种旋光性烷基二腈，这是传统上难以获得的。
• Catalytic Asymmetric Synthesis of Sterically Hindered Tertiary α-Aryl Ketones
  作者：Robert Doran、Patrick J. Guiry

  DOI：10.1021/jo5014806

  日期：2014.10.3

  The catalytic asymmetric synthesis of a series of tertiary α-aryl cyclopentanones and cyclohexanones has been accomplished via a Pd-catalyzed decarboxylative protonation of the corresponding α-aryl-β-keto allyl esters. Enantioselectivities of up to 92% ee and 74% ee were achieved for cyclopentanone and cyclohexanone substrates, respectively. The route described gives access to these important structural

  一系列叔α-芳基环戊酮和环己酮的催化不对称合成是通过相应的α-芳基-β-酮烯丙基烯丙基酯的Pd催化脱羧质子化而完成的。对映选择性高达92％ee和74％ee分别对环戊酮和环己酮底物进行了测定。所描述的途径允许以中等至高水平的对映选择性进入这些重要的结构基序。特别地，这仅仅是制备叔α-芳基环戊烷酮的第二种直接方法。合成方法允许对芳基进行简单的修饰。重要的是，含有空间位阻芳基的底物具有最高水平的对映选择性，并且这些芳基易于通过Pb介导的β-酮烯丙基酯的芳基化反应而安装。
• Photoinduced Molecular Transformations. 157. A New Stereo- and Regioselective Synthesis of 2,6-Diaryl-3,7-dioxabicyclo[3.3.0]octane Lignans Involving a .beta.-Scission of Alkoxyl Radicals as the Key Step. New Total Syntheses of (.+-.)-Sesamin, (.+-.)-Eudesmin, and (.+-.)-Yangambin
  作者：Hiroshi Suginome、Masataka Ishikawa、Kaoru Yorita、Noriaki Shimoyama、Takahiro Sasaki、Kazuhiko Orito

  DOI：10.1021/jo00115a021

  日期：1995.5

  New total syntheses of naturally occurring 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans, (+/-)-sesamin and (+/-)-eudesmin, and the first total synthesis of (+/-)-yangambin were achieved according to a general method devised by Suginome and colleagues for replacing the carbonyl group of the cyclopentanone ring with an oxygen atom to give a corresponding tetrahydrofuran ring involving a regioselective beta-scission of alkoxyl radicals; arylation of dimethyl, diallyl, or dibenzyl 3,7-dioxobicyclo[3.3.0]octane-2,6-dicarbonate (18 and 19a,b) with aryllead triacetate 9a-c, followed by dealkoxycarbonylation of the resulting arylated product 20a-f, gave 2,6-diaryl-3,7-dioxobicyclo-[3.3.0]octane 21a-c. A regioselective Baeyer-Villiger oxidation of 21a-e with m-CPBA-NaHCO3 or -K2CO3 gave the corresponding delta-lactone 22a-c, which was reduced with DIBAL to give the corresponding lactol 23a-c. The irradiation of a solution of the hypoiodite of 23a-c, generated in situ with mercury(II) oxide-iodine, in benzene with Pyrex-filtered light resulted in a regioselective beta-scission of the corresponding alkoxyl radical to give iodo formate 24a-c. Heating 24a-c in MeOH with NaBH4 gave (+/-)-sesamin (25a), (+/-)-eudesmin (25b), or (+/-)-yangambin (25c).