3-(4-Bromophenyl)-3-hydroxy-2,2-dimethylpropanal | 88903-22-4

• 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: 3-(4-Bromophenyl)-3-hydroxy-2,2-dimethylpropanal
• CAS: 88903-22-4
• 化学式: C₁₁H₁₃BrO₂
• 分子量: 257.127
• InChiKey: LFWOAUKEMQHSHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-溴-2-甲基丙醛 、 对溴苯甲醛 在 GeCl₂-dioxane 、 三苯基膦 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以91%的产率得到3-(4-Bromophenyl)-3-hydroxy-2,2-dimethylpropanal
  参考文献：
  名称：

  锗 (II) 介导的醛的还原性交叉羟醛反应：合成具有非对映控制的四元碳中心的羟醛

  摘要：

  通过锗（II）介导的叔α-溴醛与芳香醛和脂肪醛的还原交叉醛醇反应，实现了具有季碳中心的羟醛的抗选择性合成。对羟醛产物进行一锅直接还原和还原胺化，得到相应的具有立体控制的季碳中心的 1,3-二醇和 1,3-氨基醇。

  DOI：

  10.1055/s-2007-982560

文献信息

• ALDEHYDE ENOLATE. CROSS ALDOL REACTION via TIN(II) ENOLATE
  作者：Jun-ichi Kato、Teruaki Mukaiyama

  DOI：10.1246/cl.1983.1727

  日期：1983.11.5

  Tin(II) enolate, formed in situ by the oxidative addition of metallic tin to 2-bromo-2-methylpropanal, reacts with aldehydes to give β-hydroxy aldehydes in fairly good yields.

  烯醇锡 (II) 是通过将金属锡氧化加成到 2-溴-2-甲基丙醛中而原位形成的，与醛反应以相当好的产率得到 β-羟基醛。
• Organocatalysts and Methods of Use in Chemical Synthesis
  申请人：Wang Wie

  公开号：US20070244328A1

  公开（公告）日：2007-10-18

  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 CH 2 , N—R a , O, S or C═O; Y is CH 2 , N—R a , O, S or C═O, with the proviso that at least one of X or Y is CH 2 , and preferably both of X and Y are CH 2 ; R a is H, an optionally substituted C 1 -C 12 alkyl, preferably an optionally substituted C 1 -C 6 alkyl including a C 3 -C 6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; R b is H, an optionally substituted C 1 -C 12 alkyl, preferably an optionally substituted C 1 -C 6 acyclic or a a C 3 -C 6 cyclic alkyl group, CIIO, N(Me)O, CO(S)R a or the group of Formula (III). Where R c and R d are each independently H, F, Cl, an optionally substituted C 1 -C 20 alkyl, preferably an optionally substituted C 1 -C 12 alkyl, more preferably a C 1 -C 6 alkyl, and an optionally substituted aryl group, or together R c and R d form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R 1 is OH, OR, NR′R″, NHC(═O)R, NHSO 2 R; R 2 is H, F, Cl, an optionally substituted C 1 -C 20 alkyl, preferably an optionally substituted C 1 C 6 alkyl, an optionally substituted aryl group or a ═O group (which establishes a carbonyl group with the carbon to which ═O is attached; R 3 is H, OH, F, Cl, Br, I, Cl, an optionally substituted C 1 -C 20 alkyl, alkenyl or alkynyl (“hydrocarbyl”) group, preferably an optionally substituted C 1 -C 6 alkyl, or an optionally substituted aryl, such that the carbon to which R 3 is attached has an R or S configuration; R is II, an optionally substituted C 1 -C 20 alkyl, preferably an optionally substituted C 1 -C 6 alkyl, or an optionally substituted aryl group, R′ and R″ are each independently H, an optionally substituted C 1 -C 20 alkyl group, preferably an optionally substituted C 1 -C 6 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.

  本发明涉及一种包含有机催化剂的组合物，该组合物促进立体选择性反应及其合成和使用的方法。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，以及其合成和使用的方法。这些化合物具有公式（I）和（II）的结构。其中，X独立地选自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、可选取代的C1-C12烷基，最好是可选取代的C1-C6烷基，包括C3-C6环烷基，或可选取代的芳基，最好是可选取代的苯基；Rb为H、可选取代的C1-C12烷基，最好是可选取代的C1-C6非环烷基或C3-C6环烷基，CIIO、N(Me)O、CO(S)Ra或公式（III）的基团。其中，Rc和Rd各自独立地为H、F、Cl、可选取代的C1-C20烷基，最好是可选取代的C1-C12烷基，更好是C1-C6烷基，以及可选取代的芳基，或者Rc和Rd一起形成可选取代的碳环或可选取代的杂环；R1为OH、OR、NR′R″、NHC(═O)R、NHSO2R；R2为H、F、Cl、可选取代的C1-C20烷基，最好是可选取代的C1-C6烷基、可选取代的芳基或═O基团（与═O相连的碳原子上形成羰基基团）；R3为H、OH、F、Cl、Br、I、Cl、可选取代的C1-C20烷基、烯基或炔基（“烃基”）团，最好是可选取代的C1-C6烷基，或可选取代的芳基，使得R3连接的碳原子具有R或S构型；R为II、可选取代的C1-C20烷基，最好是可选取代的C1-C6烷基，或可选取代的芳基团，R′和R″各自独立地为H、可选取代的C1-C20烷基团，最好是可选取代的C1-C6烷基，或可选取代的芳基团；或者R′和R″一起形成可选取代的杂环，最好是4到7个成员的可选取代的杂环基团或与R′和R″连接的氮原子一起形成可选取代的杂环芳基环；其中所述化合物不含金属催化剂。
• KATO, JUN-ICHI;MUKAIYAMA, TERUAKI, CHEM. LETT., 1983, N 11, 1727-1728
  作者：KATO, JUN-ICHI、MUKAIYAMA, TERUAKI

  DOI：——

  日期：——
• US7968734B2
  申请人：——

  公开号：US7968734B2

  公开（公告）日：2011-06-28
• Germanium(II)-Mediated Reductive Cross-Aldol Reaction of Aldehydes: Synthesis of Aldols with Diastereocontrolled Quaternary Carbon Centers
  作者：Akio Baba、Shin-ya Tanaka、Makoto Yasuda

  DOI：10.1055/s-2007-982560

  日期：2007.7

  anti-Selective synthesis of aldols with quaternary carbon centers was achieved by germanium(II)-mediated reductive cross-aldol reaction of tertiary α-bromo aldehydes with both aromatic and aliphatic aldehydes. One-pot direct reduction and reductive amination of the aldol products were performed to give the corresponding 1,3-diol and 1,3-amino alcohol with stereocontrolled quaternary carbon centers

  通过锗（II）介导的叔α-溴醛与芳香醛和脂肪醛的还原交叉醛醇反应，实现了具有季碳中心的羟醛的抗选择性合成。对羟醛产物进行一锅直接还原和还原胺化，得到相应的具有立体控制的季碳中心的 1,3-二醇和 1,3-氨基醇。