甲氧基甲氧基乙醛 | 162468-22-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 甲氧基甲氧基乙醛
• 英文名称: methoxymethyleneoxyacetaldehyde
• 英文别名: 2-(methoxymethoxy)acetaldehyde；methoxymethyl-glycolaldehyde；methoxymethoxyacetaldehyde；methoxymethoxy-acetaldehyde；Methoxymethoxy-acetaldehyd；Acetaldehyde, (methoxymethoxy)-
• CAS: 162468-22-6
• 化学式: C₄H₈O₃
• 分子量: 104.106
• InChiKey: GAOHPGKVCIOCHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  7
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  甲氧基甲氧基乙醛 、 sodium pyruvate 在 KPi 作用下， 以69%的产率得到9=O-methyl-3,5,7-trideoxy-L-arabino-2-nonulosonic acid
  参考文献：
  名称：

  Sequential Three- and Four-Substrate Aldol Reactions Catalyzed by Aldolases

  摘要：

  This paper describes a useful synthetic strategy based on sequential enzyme-catalyzed aldol addition reactions. The aldol reaction of an acceptor aldehyde with acetaldehyde, catalyzed by 2-deoxyribose-5-phosphate aldolase (DERA, EC 4.1.2.4), gives a new aldehyde, which subsequently reacts with a second donor substrate, catalyzed by DERA or another aldolase. This sequential aldol reaction proceeds because of the formation of a stable cyclic hemiacetal or hemiketal product. In this way several 6-substituted 2,4,6-trideoxyhexoses have been stereoselectively synthesized via a one-pot double DERA-catalyzed reaction. DERA coupled with fructose-1,6-diphosphate aldolase from rabbit muscle (RAMA, EC 4.1.2.13) in a one-pot reaction gave a variety of 5-deoxyheptuloses, however not in 100% stereoselectivity. The sequential aldol reactions with four substrates were accomplished by coupling DERA with N-acetylneuraminic acid aldolase (NeuAc aldolase, EC 4.1.3.3) to give several nine-carbon sialic acid-type sugar derivatives.

  DOI：

  10.1021/ja00134a001
• 作为产物：
  描述：

  2-(methoxymethoxy)ethanol 在 四丙基高钌酸铵 N-甲基吲哚酮 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 甲氧基甲氧基乙醛
  参考文献：
  名称：

  铱催化的烯丙基取代：与催化循环相关的 IrIII 配合物的立体化学方面和分离

  摘要：

  使用 P(OPh)3 作为配体，Ir 催化的烯丙基烷基化对映体富集的单取代烯丙基乙酸酯的构型保留率高达 87%。以单齿磷酰胺作为配体，在非手性或外消旋底物的不对称烯丙基烷基化中实现了高达 86% ee 的高区域和对映选择性。N-tosylbenzylamide 锂被确定为适合烯丙基胺化的亲核试剂。特别重要的是使用氯化锂作为添加剂，通常会导致对映选择性增加。通过 X 射线晶体结构分析和光谱数据对两种 (π-烯丙基) IrIII 配合物进行了表征。

  DOI：

  10.1002/1099-0682(200210)2002:10<2569::aid-ejic2569>3.0.co;2-5

文献信息

• Conformational, steric and electronic effects on the site- and chemoselectivity of the metal-catalyzed reaction of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides
  作者：Bao Zhang、Andrew G. H. Wee

  DOI：10.1039/c2ob25103e

  日期：——

  The Rh(II)- and Cu(II)-catalyzed reactions of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides are investigated to delineate how conformational, steric and electronic factors influence the site- and chemoselectivity of the metallocarbenoid reaction. The N-bis(trimethylsilyl)methyl (N-BTMSM) group is found to be essential in promoting the metallocarbenoid reaction at the N-(2-indolyl)methyl

  研究了N-双（三甲基甲硅烷基）甲基，N-（2-吲哚基）甲基α-重氮酰胺的Rh（II）和Cu（II）催化反应，以描述构象，空间和电子因素如何影响位点和金属类化合物反应的化学选择性。所述Ñ双（三甲基硅烷基）甲基（Ñ -BTMSM）基团被发现是在促进在所述metallocarbenoid反应必需ñ - （2-吲哚基）甲基部分，以及提供有关酰胺N-C微妙但有效的构象的影响α在携带N-C重氮酯σ键α烷氧基甲基侧链，具有出色的位点和化学选择性。通常，发现金属催化的反应有利于在吲哚C（2）-C（3）双键上的金属碳氢化合物加成-C-H，从而得到环丙烷化产物（四环γ-内酰胺）。然而，化学选择性还受空间效应，如在显示Ñ - [2-（3- methylindolyl）]甲基重氮酯，以及由该催化剂所采用的性质在一定程度上，如在该N-C α-烷氧基甲基重氮酰胺。发现四环γ-内酰胺在金属碳烯化合物反应条件下或在酸性条
• Total Synthesis of (+)-4,5-Deoxyneodolabelline
  作者：David R. Williams、Richard W. Heidebrecht

  DOI：10.1021/ja0279803

  日期：2003.2.19

  allylsilane 3a with excellent diastereoselectivity. Dihydropyrans 2a and 2b were prepared from optically pure acyclic acetals via ring-closing metathesis. Coupling of 3a and 2a or 2b via the carbon-Ferrier protocol gave trans-2,6-disubstituted dihydropyrans 30 and 35 with complete stereoselectivity. Vanadium-based pinacol coupling reactions were explored for closure of the medium-sized carbocycle to yield

  海洋多标签烷二萜 (+)-4,5-脱氧新多标签碱 (1) 的首次全合成已经完成。高效方法的特点是二氢吡喃 2ab 和环戊基硅烷 3ab 的会聚组装。烯丙基硅烷 3a 是由 2-甲基-2-环戊烯酮通过铜催化的 1,4-加成和所得烯醇化物的非对映选择性烷基化制备的。外消旋环戊酮 8 的化学拆分受 (S)-CBS 催化的硼氢化物还原的影响。对映体富集的酮 8 的直接羟甲基化形成烯丙醇 14 是通过 Stille 钯催化的环戊烯基三氟甲磺酸酯 13 的交叉偶联实现的。用三甲基甲硅烷基铜试剂处理相应的烯丙基磷酸酯 15 提供了烯丙基转座置换，产生具有优异非对映选择性的环外烯丙基硅烷 3a。二氢吡喃 2a 和 2b 由光学纯的无环缩醛通过闭环复分解制备。3a 和 2a 或 2b 通过碳-Ferrier 协议偶联得到具有完全立体选择性的反式-2,6-二取代二氢吡喃 30 和 35。探索了基于钒的频哪醇偶
• Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes
  作者：Tobias Sandmeier、Simon Krautwald、Hannes F. Zipfel、Erick M. Carreira

  DOI：10.1002/anie.201506933

  日期：2015.11.23

  Fully stereodivergent dual‐catalytic α‐allylation of protected α‐amino‐ and α‐hydroxyacetaldehydes is achieved through iridium‐ and amine‐catalyzed substitution of racemic allylic alcohols with chiral enamines generated in situ. The operationally simple method furnishes useful aldehyde building blocks in good yields, more than 99 % ee, and with d.r. values greater than 20:1 in some cases. Additionally

  通过铱和胺催化的外消旋烯丙基醇被原位生成的手性烯胺取代，可以实现受保护的α-氨基和α-羟基乙醛的完全立体发散双催化α-烯丙基化。该操作简单的方法可提供有用的醛结构单元，产率高，ee大于99％，并且在某些情况下其dr值大于20：1。此外，该γ，δ-不饱和产物，可以进一步在一个stereodivergent方式以高选择性和与立体化学完整性的保存在C官能α 位置。
• Preparation of substituted aldehydes
  申请人：DU PONT

  公开号：US02286034A1

  公开（公告）日：1942-06-09

  540,133. Catalytic dehydrogenation. DU PONT DE NEMOURS CO., E. I. April 4, 1940, No. 6087. Convention date, April 4, 1939. [Class 1 (i)] [Also in Group IV] Oxy-aldehydes are produced by passing over a de-hydrogenating catalyst the vapour of a glycol ether or ester of the formula CH 2 OXCH,OH where X is an alkyl, alkoxy-alkyl, aryl, aralkyl, phenoxy-alkyl or acyl group. The re-action temperature may be 200-375‹C. and the pressure may be atmospheric or above, such as 5-1000 atmospheres. Preferably a diluent is used, such as steam, nitrogen or carbon dioxide. Suitable catalysts may be made by fusing copper oxide alone or with another oxide such as magnesium or nickel oxide and reducing the mass; or copper-nickel copper-silicon, copper-zinc chromate and copper-zinc oxide catalysts may be made by precipitation and reduction. Nickel with or without cerium may be used under mild conditions. In examples 1-3 methoxy-acetaldehyde is produced from glycol monomethyl ether by means of the following catalysts:- (a) a reduced mixture of copper oxide, silica and chromium oxide (Cr O 3 ) in the molar ratio 100:10:5; (b) a similar mixture in the ratio 100:50:10; and (c) reduced copper oxide and silica in the ratio 9:1. In example 4 methoxy-methoxy-acetaldehyde is produced from methoxy-methoxy-ethanol, using the catalyst of example 1; and in example 5 acetoxy-acetaldehyde is produced from glycolmonoaceate by the same catalyst.

  540,133. 催化脱氢。杜邦公司，E. I. 1940年4月4日，编号6087。公约日期为1939年4月4日。[1类（i）] [也属于第四组] 通过将甘油醚或酯的蒸汽经过脱氢催化剂制得氧醛，其中甘油醚或酯的化学式为CH2OXCH,OH，其中X为烷基、烷氧基烷基、芳基、芳基烷基、苯氧基烷基或酰基。反应温度可为200-375°C，压力可为大气压或以上，如5-1000大气压。最好使用稀释剂，如蒸汽、氮气或二氧化碳。适用的催化剂可由熔化氧化铜单独或与镁或氧化镍等其他氧化物混合并还原所制备；或者可通过沉淀和还原制备铜-镍、铜-硅、铜-锌铬酸盐和铜-锌氧化物催化剂。镍在温和条件下可与铈一同使用。在示例1-3中，通过以下催化剂从甘油单甲醚制备甲氧基乙醛：（a）铜氧化物、二氧化硅和氧化铬（CrO3）的还原混合物，摩尔比为100:10:5；（b）类似比例的混合物，比例为100:50:10；以及（c）还原的铜氧化物和二氧化硅，比例为9:1。在示例4中，通过使用示例1的催化剂从甲氧基甲氧基乙醇制备甲氧基甲氧基乙醛；在示例5中，通过使用相同的催化剂从甘油单乙酸酯制备乙酰氧基乙醛。
• Convenient preparation of synthetically useful chiral quaternary carbon-containing bicyclic compounds with organocatalysts
  作者：Yuichiro Kawamoto、Naoki Noguchi、Daiki Ozone、Toyoharu Kobayashi、Hisanaka Ito

  DOI：10.1016/j.tetlet.2021.153495

  日期：2021.11

  Chiral quaternary carbon-containing bicyclic compounds possessing carbonyl functionalities were efficiently synthesized through asymmetric intramolecular aldol reactions with organocatalysts. Bicyclo [3.3.0] and [3.4.0] systems were constructed with a diamine catalyst, while bicyclo [4.3.0] and [4.4.0] skeletons were prepared by an acylsulfonamide type catalyst.

  通过与有机催化剂的不对称分子内醛醇反应有效地合成了具有羰基官能团的手性含季碳双环化合物。双环[3.3.0]和[3.4.0]体系由二胺催化剂构建，而双环[4.3.0]和[4.4.0]骨架由酰基磺酰胺型催化剂制备。