2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]propanal | 78957-71-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]propanal
• 英文别名: 2-((tert-butyldiphenylsilyl)oxy)propanal；2-(tert-butyldiphenylsiloxy)propanal；(O-diphenyl-tert-butylsilyl)lactaldehyde；2-(Tert-butyldiphenylsilyloxy)propan-1-one；2-[tert-butyl(diphenyl)silyl]oxypropanal
• CAS: 78957-71-8
• 化学式: C₁₉H₂₄O₂Si
• 分子量: 312.484
• InChiKey: RRMPJLZPEZKPND-UHFFFAOYSA-N

物化性质

• 沸点：
  357.6±34.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]propanal 在 吡啶 、 正丁基锂 、 sodium hydride 、 lithium diisopropyl amide 作用下， 反应 9.58h， 生成 (2S,3S,4S)-2-((R)-1-Acetoxy-ethyl)-3-benzylamino-4-(tert-butyl-diphenyl-silanyloxy)-pentanoic acid tert-butyl ester
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d
• 作为产物：
  描述：

  ethyl 2-((tert-butyldiphenylsilyl)oxy)propanoate 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 1.58h， 生成 2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]propanal
  参考文献：
  名称：

  Highly Diastereoselective Conjugate Addition of Lithium Dialkylamides to α,β-Unsaturated Esters Having a Chiral Center at the γ-Position

  摘要：

  The conjugate addition of lithium amides 2 to tert-butyl 4-(OR)-substituted-2-pentenoates 1 produced a mixture of the syn-and anti-amino esters (3 and 4) in high yields. Sterically bulky OR groups, such as trityloxy and tert-butyldiphenylsilyloxy, gave the syn diastereomer 3 either exclusively or predominantly. The syn-selectivity may be explained by a modified Felkin-Anh model. The use of tert-butyldimethylsilyloxy as an OR group afforded a nearly 1:1 mixture of diastereoisomers, and the use of the smallest MeO group produced a 63:37 mixture of the syn 3 and anti isomer 4. The presence of Me group at the alpha-position (C-2 position) of the enoate enhanced the syn diastereoselectivity up to 100%; the conjugate addition to tert-butyl 4-methoxy-2-methyl-2-pentenoate (17) gave the syn-isomer 18 exclusively. This enhancement may be explained by the combination of chelation and allylic strain model 19 in which the smallest H orients inside to avoid an allylic strain. A phenyl group at the gamma-position enhanced the anti selectivity in the case of gamma-alkoxy-alpha,beta-enoates such as isopropyl 4-[(tert-butyldimethylsilyl)oxy]-4-phenyl-2-buteonoate (20), and in the case of gamma-alkyl-alpha,beta-enoates such as tert-butyl 4-phenyl-2-pentenoate (27).

  DOI：

  10.1021/jo970435d

文献信息

• Carbenylative Amination and Alkylation of Vinyl Iodides via Palladium Alkylidene Intermediates
  作者：Ilandari Dewage Udara Anulal Premachandra、Thi A. Nguyen、Chengtian Shen、Eugene S. Gutman、David L. Van Vranken

  DOI：10.1021/acs.orglett.5b02820

  日期：2015.11.6

  palladium-catalyzed reactions involving insertion of alkylidenes with α-hydrogens undergo β-hydride elimination from alkylpalladium(II) intermediates to form alkenes. Vinyl iodides were shown to generate η3-allylpalladium intermediates that resist β-hydride elimination, preserving the sp3 center adjacent to the carbene moiety. Acyclic stereocontrol (syn/anti) for carbenylative amination and alkylation reactions was

  大多数涉及亚烷基与α氢插入的钯催化反应都会从烷基钯（II）中间体中进行β-氢化物消除，从而形成烯烃。碘代乙烯显示出生成η 3个抵抗β-氢消除π-烯丙基中间体，保留SP 3邻近碳烯部分中心。用于羰基化胺化和烷基化反应的无环立体控制（syn / anti）很低，这表明在迁移插入步骤中缺乏控制。受阻严重的卡宾前体莫名其妙地导致形成具有高水平立体控制的Z-烯烃。
• Efficient synthesis of syn -α-alkoxy epoxide via a diastereoselective Darzens reaction
  作者：Kosaku Tanaka、Kenichi Kobayashi、Kazuhiko Takatori、Hiroshi Kogen

  DOI：10.1016/j.tet.2017.02.051

  日期：2017.4

  A highly diastereoselective Darzens reaction was developed by using a MEM- or TBDPS-protected α-hydroxy aldehyde with di-tert-butyl bromomalonate. This method effectively provides a syn-α-alkoxy epoxide, and a possible reaction mechanism was proposed to explain the high syn selectivity.

  通过使用MEM或TBDPS保护的α-羟基醛与溴化马来酸二叔丁酯开发了高度非对映选择性的Darzens反应。该方法有效地提供了顺式-α-烷氧基环氧化物，并提出了可能的反应机理来解释高的顺式选择性。
• Synthesis of Enantiomerically and Diastereomerically Pure 4-Hydroxy-1,2-alkadienyl Carbamates and Their Application in a Modified Nazarov Cyclization Towards Chiral Cyclopentenones
  作者：Dieter Hoppe、Maik Zimmermann、Birgit Wibbeling

  DOI：10.1055/s-2004-816002

  日期：——

  The addition of racemic titanated alkynyl N,N-diisopropylcarbamates onto enantiopure α-dibenzylamino- or a-silyloxyalkanals affords two (out of four possible) diastereomeric, enantiopure 5-hetero-substituted 4-hydroxy-1,2-alkadienyl carbamates. As demonstrated for hydroxyallenes 23 and 24, the reaction sequence for modified Nazarov cyclization according to Tius, yields stereohomogeneous, highly substituted

  将外消旋的钛化炔基 N,N-二异丙基氨基甲酸酯添加到对映纯的 α-二苄基氨基-或α-甲硅烷氧基链烷醛上，得到两种（四种可能的）非对映体、对映纯 5-杂取代的 4-羟基-1,2-链二烯基氨基甲酸酯。正如羟基丙二烯 23 和 24 所证明的，根据 Tius 进行改性 Nazarov 环化的反应序列产生立体均相、高度取代的 5-亚烷基-2,3-二烷基-4-苯基-2-环戊烯-1-酮 (Z,R) -25 和 (E, R)-26。
• 1,2-Asymmetric induction in the aldol addition reaction of malonate ester enolate to α-alkoxy aldehyde
  作者：Shinji Marumoto、Hiroshi Kogen、Shunji Naruto

  DOI：10.1039/a806290k

  日期：——

  Stereoselective aldol reactions between the lithium enolate of tert-butyl malonate and various α-alkoxy aldehydes in the presence of zinc chloride gave anti-1,2-diols in high yields; 2-trityloxypropanal yielded the syn-1,2-diol under the same conditions.

  在氯化锌存在下，丙二酸叔丁酯的锂烯醇盐与各种δ-烷氧基醛发生立体选择性醛醇反应，得到了高产率的反-1,2-二醇；在相同条件下，2-三苯甲基氧基丙醛得到了合成-1,2-二醇。
• Stereocontrolled formation of spiro enones by radical cyclization of bromo acetals
  作者：Derrick L.J. Clive、Xiaojun Huang

  DOI：10.1016/s0040-4020(01)00226-5

  日期：2001.4

  reduction and treatment of the resulting alcohols with ethyl vinyl ether in the presence of NBS gives bromo acetals (e.g. 11) that undergo 5-exo-trigonal radical cyclization, affording compounds that are easily converted into spiro enones (e.g. 16). The stereochemistry at the spiro center is controlled by the stereochemistry at the hydroxyl-bearing carbon of the intermediate alcohol.

  酮与2-[[（（1,1-（二甲基乙基）二苯基甲硅烷基]氧基]丙醛进行醛醇缩合（7），脱水，NaBH 4还原并在NBS存在下用乙基乙烯基醚处理所得醇，得到溴代乙缩醛（例如11）经历5-外三角自由基环化，得到易于转化为螺烯酮的化合物（例如16），螺中心的立体化学由中间体醇的含羟基碳上的立体化学控制。