2-methyl-2-(phenylseleno)propionaldehyde | 65946-61-4

• 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: 2-methyl-2-(phenylseleno)propionaldehyde
• 英文别名: α-(phenylseleno)isobutyraldehyde；α-phenylselenoisobutyraldehyde；2-methyl-2-(phenylselenenyl)propanal；2-methyl-2-(phenylselenyl)propanal；Methyl(phenylseleno)-2 propanal；Propanal, 2-methyl-2-(phenylseleno)-；2-methyl-2-phenylselanylpropanal
• CAS: 65946-61-4
• 化学式: C₁₀H₁₂OSe
• 分子量: 227.165
• InChiKey: CIBCHMBCMQQDTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.41
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-2-(phenylseleno)propionaldehyde 以 四氢呋喃 、 甲苯 为溶剂， 反应 14.0h， 生成 N-benzyl-2-methyl-2-(phenylselanyl)hex-5-en-3-amine
  参考文献：
  名称：

  α-Phenylselanyl imines: preparation of β-phenylselanyl amines and original synthesis of allylaziridines

  摘要：

  Resorting to suitable methods, a wide variety of alpha-phenylselanyl imines 2-5 were prepared from alpha-phenylselanyl aldehydes and alpha-phenylselanyl ketones 1. These compounds were reduced to afford beta-phenylselanyl amines 6-9. Our experimental conditions have limited the well known deselenenylation side-reaction occurring with most hydrides. On the other hand, the reaction of alpha-phenylselanyl imines 2 with organometallics led to the expected addition products only in the case of allylated derivatives. Depending on the temperature, either alpha-phenylselanyl amines 11 or unexpected allylaziridines 12 were recovered. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.10.065
• 作为产物：
  描述：

  N,N,N-triphenylselenylisocyanuric acid 、 异丁醛 在 L-脯氨酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以75%的产率得到2-methyl-2-(phenylseleno)propionaldehyde
  参考文献：
  名称：

  N,N,N-三苯基硒基异氰尿酸 (TPSCA)：一种用于醛和酮的 α-苯基硒基化的新型多功能试剂

  摘要：

  已制备、表征并用作亲电子苯基硒基的来源，新的、多功能的试剂 N , N , N - 三苯基硒基异氰脲酸 (TPSCA)。这种相对稳定的化合物用于在温和的反应条件下由 l-脯氨酰胺催化的醛和酮的有效 α-硒基化反应。还研究了醛的有机催化不对称 α-硒基化反应，发现该反应以高对映选择性（96% ee）进行。

  DOI：

  10.1055/s-0035-1560051

文献信息

• [EN] ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS<br/>[FR] ORGANOCATALYSEURS ET PROCEDES D'UTILISATION DE CES DERNIERS DANS LA SYNTHESE CHIMIQUE
  申请人：STC UNM

  公开号：WO2006007586A1

  公开（公告）日：2006-01-19

  The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-­selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R', NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1­C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ('hydrocarbyl') group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R' are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R' are attached; and wherein said compound is free from a metal catalyst.

  本发明涉及一般包括有机催化剂的组合物，该催化剂促进立体选择性反应以及其合成和使用方法。特别地，本发明涉及无金属有机催化剂以促进立体选择性反应，以及其合成和使用方法。这些化合物具有以下结构的式（I）和（II）。其中X独立地选择自CH2、N-Ra、O、S或C=O；Y为CH2、N-Ra、O、S或C=O，但至少X或Y中的一个为CH2，最好是X和Y都为CH2；Ra为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6烷基，包括C3-C6环烷基，或可选择地取代的芳基，最好是可选择地取代的苯基；Rb为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6无环或C3-C6环烷基，CHO、N(Me)O、CO(S)Ra或式（III）的基团。其中Rc和Rd各自独立地为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C12烷基，更好地是C1-C6烷基，以及可选择地取代的芳基，或者Rc和Rd一起形成可选择地取代的碳环或可选择地取代的杂环；R1为OH、OR、NR'R'、NHC(=O)R、NHSO2R；R2为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，可选择地取代的芳基或=O基团（与=O连接的碳形成羰基基团）；R3为H、OH、F、C1、Br、I、Cl、可选择地取代的C1-C20烷基、烯基或炔基（'烃基'），最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，使得R3连接的碳具有R或S构型；R为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，R'和R'各自独立地为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基；或者R'和R'一起形成可选择地取代的杂环，最好是4到7成员的可选择地取代的杂环基团或与R'和R'连接的氮原子形成可选择地取代的杂芳基环；其中所述化合物不含金属催化剂。
• K₂S₂O₈-promoted C–Se bond formation to construct α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds
  作者：Xue-Yan Yang、Ruizhe Wang、Lu Wang、Jianjun Li、Shuai Mao、San-Qi Zhang、Nanzheng Chen

  DOI：10.1039/d0ra05927g

  日期：——

  oxidant in the absence of catalyst and afford desired products in moderate to excellent yields. This protocol provides a very simple route for the synthesis of α-phenylseleno carbonyl compounds and α,β-unsaturated carbonyl compounds.

  已经开发了一种新的 K 2 S 2 O 8促进中性条件下交叉偶联形成的 C-Se 键。在没有催化剂的情况下，使用 K 2 S 2 O 8作为氧化剂，多种醛和酮反应良好，并以中等至优异的产率提供所需的产物。该协议为合成α-苯基硒羰基化合物和α、β-不饱和羰基化合物提供了一条非常简单的路线。
• Synthesis of Enantiomerically Pure Mono-, Di- and Trisubstituted 2-Sulfinylbuta-1,3-dienes, via β-Hydroxy Selenides
  作者：Pascal Gosselin、Eric Bonfand、Christian Maignan

  DOI：10.1055/s-1996-4348

  日期：1996.9

  α-Lithiated (+)-(R)-para-tolyl vinyl sulfoxide reacts with α-selanyl-carbonyl compounds to give the corresponding β-hydroxy selenides. Subsequent Krief-Reich elimination affords enantiomerically pure mono-, di- and trisubstituted 2-sulfinylbuta-1,3-dienes.

  α-锂化的(+)-(R)-对甲苯基乙烯亚砜与含α-硒醚碳基化合物反应，生成相应的β-羟基硒化物。随后的Krief-Reich消除反应得到了手性纯净的单、双和三取代的2-亚砜基丁-1,3-二烯。
• A Simple and Efficient <scp>l</scp>-Prolinamide-Catalyzed α-Selenenylation Reaction of Aldehydes
  作者：Wei Wang、Jian Wang、Hao Li

  DOI：10.1021/ol0488946

  日期：2004.8.1

  An efficient and simple l-prolinamide-catalyzed alpha-selenenylation reaction of aldehydes with N-(phenylseleno)phthalimide has been developed for the efficient preparation of alpha-phenylselenoaldehydes. Such compounds are versatile building blocks for the synthesis of alpha,beta-unsaturated aldehydes, allylic alcohols, and amines. [reaction: see text]

  已经开发了醛与N-（苯基硒代）邻苯二甲酰亚胺的有效且简单的1-脯氨酰胺催化的醛的α-硒烯化反应，用于有效制备α-苯基硒代醛。这样的化合物是用于合成α，β-不饱和醛，烯丙基醇和胺的通用结构单元。[反应：看文字]
• Total synthesis and stereochemical determination of yoshinone A
  作者：Seiichi Shinomiya、Arihiro Iwasaki、Osamu Ohno、Kiyotake Suenaga

  DOI：10.1016/j.phytochem.2016.10.005

  日期：2016.12

  and therefore is expected to be a lead compound for obesity drugs. To establish its absolute configuration, and to provide sufficient amounts for further research, the total synthesis of yoshinone A was achieved through synthesis of its two possible diastereomers.

  2014 年，从海洋蓝藻 Leptolyngbya sp. 中分离出含有 γ-吡喃酮的聚酮化合物 yoshinone A。并确定了其结构。Yoshinone A 抑制 3T3-L1 细胞向脂肪细胞的分化，EC50 值为 420 nM，没有任何细胞毒性，因此有望成为肥胖药物的先导化合物。为了确定其绝对构型，并为进一步研究提供足够的数量，yoshinone A 的全合成是通过合成其两种可能的非对映异构体来实现的。