2-(benzo[1,3]dioxol-5-yl)chroman | 250660-51-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: 2-(benzo[1,3]dioxol-5-yl)chroman
• 英文别名: 4'-Methylenedioxyflavan；2-(1,3-benzodioxol-5-yl)-3,4-dihydro-2H-chromene
• CAS: 250660-51-6
• 化学式: C₁₆H₁₄O₃
• 分子量: 254.285
• InChiKey: ZSQCZTKFWUOWLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4'-methoxyflav-2-ene 、 2-(benzo[1,3]dioxol-5-yl)chroman 在 iron(III) chloride hexahydrate 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (E)-11-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-5a-(4-methoxyphenyl)-5a,11,11a,12-tetrahydrochromeno[2,3-b]chromene 、 (E)-11-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-5a-(4-methoxyphenyl)-5a,11,11a,12-tetrahydrochromeno[2,3-b]chromene
  参考文献：
  名称：

  Iron-Catalyzed Rearrangements and Cycloaddition Reactions of 2H-Chromenes

  摘要：

  Iron(III) salts catalyze the tandem rearrangement/hetero-Diels-Alder reaction of 2H-chromenes to yield tetrahydrochromeno heterocycles. The process can occur as a homodimerization and cycloaddition process using electron-rich dienophiles. Deuterium labeling and mechanistic studies revealed a hydride shift and ortho-quinone methide cycloaddition reaction pathway.

  DOI：

  10.1021/ol202772k
• 作为产物：
  描述：

  3,4-亚甲二氧苯乙酮 在 potassium carbonate 、 对甲苯磺酰肼 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 乙醇 、 水 为溶剂， 反应 5.0h， 生成 2-(benzo[1,3]dioxol-5-yl)chroman
  参考文献：
  名称：

  Tosylhydrazine mediated conjugate reduction and sequential reductive coupling cyclization: synthesis of 2-arylchromans

  摘要：

  Tosylhydrazine mediated conjugate reduction of 2-hydroxyl chalcones and sequential reductive coupling cyclization is described. This is an unprecedented protocol and an extremely efficient method for a one-pot domino synthesis of 2-arylchromans in good to excellent yields from commercially available, cheap starting materials. More importantly, the two-step reactions can be easily controlled to afford dihydrochalcones or 2-arylchromans by the mole amounts of tosylhydrazine. Furthermore, the operational simplicity of the process and the high functional group tolerance are remarkable. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.08.027

文献信息

• One pot tandem dual CC and CO bond reductions in the β-alkylation of secondary alcohols with primary alcohols by ruthenium complexes of amido and picolyl functionalized N-heterocyclic carbenes
  作者：A. P. Prakasham、Sabyasachi Ta、Shreyata Dey、Prasenjit Ghosh

  DOI：10.1039/d1dt02849a

  日期：——

  investigation performed on two representative catalytic substrates, 1-phenylethanol and benzyl alcohol using the neutral ruthenium (1c) complex showed that the catalysis proceeded via a partially reduced CC hydrogenated carbonyl species, [PhCOCH2CH2Ph] (3′), to the fully reduced CO and CC hydrogenated secondary alcohol, [PhCH(OH)CH2CH2Ph] (3). Furthermore, the time dependent study showed that the major product

  两种不同类别的钌配合物，即 [1-mesityl-3-(2,6-Me 2 - phenylacetamido)-imidazol -2- ylidene ]Ru( p- cymene)Cl ( 1c ) 和 [1-(pyridin -2-ylmethyl)-3-(2,6-Me 2 - phenyl)-imidazol -2- ylidene ]Ru( p- cymene)Cl}Cl ( 2c ), 成功催化了一锅串联醇-醇偶联反应的各种仲和伯醇的，在中度至良好的产率CA。63–89%。使用中性钌 ( 1c ) 配合物对两种代表性催化底物 1-苯基乙醇和苯甲醇进行的机理研究表明，催化是通过部分还原的 CC 氢化羰基物质 [PhCOCH 2 CH 2 Ph] ( 3' )，转化为完全还原的CO 和 C C 氢化仲醇 [PhCH(OH)CH 2 CH 2 Ph] ( 3 )。此外，时间依赖性研究表明，在120
• A Modular Synthesis of 2-Alkyl- and 2-Arylchromans via a Three-Step Sequence
  作者：Robert Orr、Louis-Charles Campeau、Harry Chobanian、Jamie McCabe Dunn、Barbara Pio、Christopher Plummer、Andrew Nolting、Rebecca Ruck

  DOI：10.1055/s-0036-1588075

  日期：——

  2-alkylchromans, as well as an azachroman derivative. The asymmetric version of this approach via a Noyori-catalyzed ketone reduction and subsequent cyclization is likewise highlighted. A convergent three-step method for the synthesis of 2-substituted chromans is described. These results have been accomplished via the Heck coupling of readily accessible allylic alcohols and 2-iodophenols, followed by reduction and

  摘要 描述了一种用于合成2-取代的苯并二氢吡喃的收敛三步法。这些结果通过容易获得的烯丙醇和2-碘苯酚的Heck偶联，然后还原和Mitsunobu环化完成。该方法的实用性和通用性通过一系列2-芳基，2-杂芳基和2-烷基苯并二氢吡喃以及氮杂苯并二氢吡喃衍生物的合成得到证明。同样强调了通过Noyori催化的酮还原和随后的环化反应的这种方法的不对称形式。 描述了一种用于合成2-取代的苯并二氢吡喃的收敛三步法。这些结果通过容易获得的烯丙醇和2-碘苯酚的Heck偶联，然后还原和Mitsunobu环化完成。该方法的实用性和通用性通过一系列2-芳基，2-杂芳基和2-烷基苯并二氢吡喃以及氮杂苯并二氢吡喃衍生物的合成得到证明。同样强调了通过Noyori催化的酮还原和随后的环化反应的这种方法的不对称形式。
• Tandem Cross Coupling Reaction of Alcohols for Sustainable Synthesis of β-Alkylated Secondary Alcohols and Flavan Derivatives
  作者：Sujan Shee、Bhaskar Paul、Dibyajyoti Panja、Bivas Chandra Roy、Kaushik Chakrabarti、Kasturi Ganguli、Ayan Das、Gourab Kanti Das、Sabuj Kundu

  DOI：10.1002/adsc.201700722

  日期：2017.11.23

  efficiently under solvent-free conditions. Remarkably, this catalytic system disclosed so far the highest TON of 288000 for the cross coupling of alcohols. Notably, this methodology was successfully applied for the one-pot synthesis of a range of flavan derivatives. A detailed DFT studies and kinetic experiments were performed to understand the reaction mechanism as well as the high reactivity of this

  据报道，Ru（II）NHC络合物（负载量低至0.001 mol％）催化了多种芳族，脂族和杂环醇的交叉偶联。该方案在无溶剂条件下也能有效发挥作用。显着地，该催化体系公开了迄今为止用于醇的交叉偶联的最高TON为288000。值得注意的是，该方法已成功用于一系列黄烷衍生物的一锅合成。进行了详细的DFT研究和动力学实验，以了解该催化体系的反应机理以及高反应活性。
• Transition metals catalyzed C–C and C–O bonds formation: facile synthesis of flavans and benzoxepines
  作者：B. Venkat Ramulu、L. Mahendar、J. Krishna、A. Gopi Krishna Reddy、B. Suchand、G. Satyanarayana

  DOI：10.1016/j.tet.2013.05.046

  日期：2013.9

  A simple and practical method has been developed based on intermolecular [Pd]-catalyzed C–C and an intramolecular [Cu]-catalyzed C–O bond formations for the synthesis of flavans and benzoxepines. Interestingly, the method is amenable for the synthesis of a wide variety of flavans and benzoxepines with dense functionalities on aromatic moieties. Significantly, flavans and benzoxepines are present as

  基于分子间[Pd]催化的C–C和分子内[Cu]催化的C–O键的形成，开发了一种简单而实用的方法，用于合成黄烷和苯并氧杂松。有趣的是，该方法适用于合成在芳族部分上具有致密官能团的多种黄烷和苯并二氢吡啶。值得一提的是，黄烷和苯并xepine以许多生物活性天然产物的核心/部分结构形式存在。
• One pot tandem dehydrogenative cross-coupling of primary and secondary alcohols by ruthenium amido-functionalized 1,2,4-triazole derived N-heterocyclic carbene complexes
  作者：Anuj Kumar、Sabyasachi Ta、Chandrasekhar Nettem、Joseph M. Tanski、Gopalan Rajaraman、Prasenjit Ghosh

  DOI：10.1039/d2ra05531g

  日期：——

  mechanism completely, and the mechanisms adapted are divided categorically into three steps (i) nucleophilic substitution of chloride ions by alcohols, (ii) dehydrogenation of primary and secondary alcohols, and (iii) olefin and ketone hydrogenation. Our mechanistic study reveals that the formation of a deprotonated Ru–alcoholate (A) or (E) intermediate is favorable compared to the protonated form (A′)

  三个钌配合物[1-( R )-4- N- (呋喃-2-基甲基)乙酰胺基-1,2,4-三唑-5-亚基催化伯醇和仲醇的一锅串联脱氢交叉偶联反应]Ru( p-伞花烯)Cl [R = Et ( 1b ), i-Pr ( 2b ), Bn ( 3b )]，是酰胺基官能化的 1,2,4-三唑衍生的 N-杂环卡宾 (NHC) 配体。对钌 ( 1b ) 预催化剂采用密度泛函理论 (DFT) 计算，以完全理解该反应机理，所采用的机理可分为三个步骤 (i) 氯离子被醇进行亲核取代，(ii) 伯脱氢和仲醇，以及(iii)烯烃和酮氢化。我们的机理研究表明，与 ( 1b ) 中通过缔合亲核取代形成的质子化形式 ( A' ) 或 ( E' ) 相比，去质子化的 Ru-醇化物 ( A ) 或 ( E ) 中间体的形成更有利。尽管通过 ( A' ) 或 ( E' ) 进行的离子途径在脱氢和烯烃/酮氢化步骤中的势垒比通过 (