(E)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene | 168111-14-6

• 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: (E)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene
• 英文别名: (E)-1-(tert-butyldimethylsilyloxy)-3-(tributylstannyl)-but-1-ene；(E)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-but-1-ene；tert-butyl-dimethyl-[(E,3S)-3-tributylstannylbut-1-enoxy]silane
• CAS: 168111-14-6；145278-57-5
• 化学式: C₂₂H₄₈OSiSn
• 分子量: 475.418
• InChiKey: MMEIBUWRTNLUNH-HUMMXKGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.76
• 重原子数：
  25
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene 在 magnesium bromide 作用下， 生成 (2S,3R,4S)-2-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-4-phenylmethoxypentanal
  参考文献：
  名称：

  Lewis Acid Promoted Additions of .gamma.-Alkoxy- and -(Silyloxy)crotylstannanes to (S)-2-(Benzyloxy)propanal

  摘要：

  Additions of the gamma-oxygenated allylic stannane MOM ethers (R)-1a, (S)-1a, and silyl ethers (R)-1b, (S)-1b to (S)-2-(benzyloxy)propanal (2) in the presence of BF3.OEt(2) and MgBr2 were examined in order to establish matched and mismatched preferences. In the BF3 reactions, stannanes (R)-1a and (R)-1b were matched with 2. The former gave the syn adduct 3 and the cyclopropane 4 as a 93:7 mixture. The OTBS stannanes (R)-1b and (S)-1b gave only the syn adducts 7 and 9, respectively. However, in each case considerable cyclopropane adduct, 8 and 10 respectively, was also formed. When aldehyde 2 was treated with excess racemic stannane, (RS)-1a, adduct 3 derived from (R)-1a was the major product, whereas with (RS)-1b, products 7 and 8 derived from (R)-1b were formed preferentially. Aldehyde 2 showed a preference for MOM ether (S)-1a in the MgBr2-promoted reaction, but each of the enantiomeric OTBS stannanes (R)-1b and (S)-1b afforded a single product, the (Z)-syn,syn alcohol 13 from the former and the (E)-syn,syn. alcohol 9 from the latter. With excess (RS)-1b, aldehyde 2 reacted fastest with (R)-1b, in contrast to the MOM analogue(RS)-1a. The racemic (E) stannanes (E)-1a and (E)-1b were likewise examined. In the BF3 reaction, the major products (5 from the MOM ether (E)-1a and 9 from the silyl ether (E)-1b) were derived from the (R)-enantiomer. With MgBr2, the OMOM stannane (E)-1a gave rise to a mixture of four adducts arising from both the (R) and (S) enantiomers of the stannane. The OTBS stannane (E)-1b, on the other hand, afforded mainly adduct 9 derived from the (R) enantiomer of stannane (E)-1b.

  DOI：

  10.1021/jo00104a046
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (E)-3-(tributylstannyl)acrylaldehyde 、 dilithium dimethylcyanocuprate 在 六甲基磷酰三胺 作用下， 以 not given 为溶剂， 生成 (Z)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene 、 (E)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene
  参考文献：
  名称：

  γ-苄氧基烯丙基烯烃与亚环己基甘油醛的反应活性

  摘要：

  在三氟化硼的存在下，通过烷基氰基戊酸酯与3,3-二苄氧基-1-三丁基锡烷基丙-1-烯的S N 2'反应，以50-80％的产率获得苄氧基烯丙基三丁基锡。他们在不同的路易斯酸存在下与亚环己基甘油醛反应，并通过与真实的醛糖苷酶比较，在臭氧分解/脱保护序列后明确鉴定了所获得的非对映异构体加合物。简要讨论了机理以及试剂构型与烯丙基锡化反应选择性的关系。

  DOI：

  10.1016/s0022-328x(00)00928-1

文献信息

• Preparation of γ-siloxyallyltributylstannanes and their use in the synthesis of (±)-1-deoxy-6,8a-di-epi-castanospermine
  作者：Floris Chevallier、Erwan Le Grognec、Isabelle Beaudet、Florian Fliegel、Michel Evain、Jean-Paul Quintard

  DOI：10.1039/b409507c

  日期：——

  gamma-siloxyallyltributylstannanes were selectively obtained as E or Z isomers from beta-tributylstannylacrolein upon reaction with lithium or magnesium alkylcyanocuprates. The ability of the reagents to give a high syn selectivity when added to iminium salts has been used for the efficient synthesis of (+/-)-1-deoxy-6,8a-di-epi-castanospermine from succinimide. The key step of the synthesis was the

  γ-甲硅烷氧基烯丙基三丁基锡烷酸酯在与氰基氰基锂或镁发生反应后，从β-三丁基锡丙烯醛中选择性地以E或Z异构体形式获得。当将试剂添加到亚胺盐中时，该试剂产生高同位选择性的能力已被用于从琥珀酰亚胺有效合成（+/-）-1-脱氧-6,8a-二-表-泛精胺。合成的关键步骤是N-烯丙基铝中间体的烯丙基锡化，然后进行闭环复分解。
• syn-Allylstannation of N-Acyliminium Intermediates by Tributyl[γ-(silyloxy)allyl]stannanes: A Key Reaction for the Diastereoselective Synthesis of Polyhydroxypiperidines and Polyhydroxyazepanes
  作者：Floris Chevallier、Alexandre Lumbroso、Isabelle Beaudet、Erwan Le Grognec、Loïc Toupet、Jean-Paul Quintard

  DOI：10.1002/ejoc.201100302

  日期：2011.8

  The allylstannation of N-alkenyl N-acyliminium intermediates by tributyl[gamma-(silyloxy)allyl]stannanes afforded the expected adducts with a high syn-selectivity (up to 99: 1). Ensuing ring-closing metathesis afforded dehydropiperidines or dehydroazepanes which were engaged in a stereoselective dihydroxylation reaction leading to polyhydroxypiperidines or polyhydroxyazepanes in good yields. This sequence

  N-烯基N-酰基胺中间体通过三丁基[γ-(甲硅烷氧基)烯丙基]锡烷的烯丙基锡化提供了具有高顺式选择性(高达99:1)的预期加合物。随后的闭环复分解得到脱氢哌啶或脱氢氮杂环庚烷，它们参与立体选择性二羟基化反应，以良好的产率得到多羟基哌啶或聚羟基氮杂环庚烷。该序列被应用于 (+/-)-1-脱氧古洛糖野尻霉素的非对映选择性合成。
• Addition of γ-silyloxyallyltins on ethyl glyoxylate: evaluation of the influence of the experimental conditions on the stereochemical course of the reaction
  作者：Alexandre Lumbroso、Piotr Kwiatkowski、Anna Blonska、Erwan Le Grognec、Isabelle Beaudet、Janusz Jurczak、Slawomir Jarosz、Jean-Paul Quintard

  DOI：10.1016/j.tet.2009.12.037

  日期：2010.2

  Ethyl glyoxylate was reacted with α-substituted γ-(t-butyldimethylsilyloxy)-allyltributyltin in order to obtain selectively each diastereomer of ethyl 3-(t-butyldimethylsilyloxy)-2-hydroxyhex-4-enoate and subsequently the corresponding diols. Diastereomers syn-E, anti-E and anti-Z were obtained in good yields with good to high selectivities and the obtained results were rationalized by consideration

  使乙醛酸乙酯与α-取代的γ-（叔丁基二甲基甲硅烷氧基）-烯丙基三丁基锡反应，以便选择性地获得3-（叔丁基二甲基甲硅烷氧基）-2-羟基己基-4-烯酸酯的每个非对映异构体，然后得到相应的二醇。非对映体顺式- ë，抗- Ë和抗- ž与良好的高选择性和获得的结果良好的收益率在协议被考虑，环状或开过渡态的合理化与实验条件和起始试剂的结构中获得。
• Interconversion of Nonracemic .alpha.-OTBS Crotyl and .gamma.-OTBS Methallyl Tri-n-butylstannanes. Additions of the (E)-Methallyl Isomer to Representative Aldehydes
  作者：James A. Marshall、Jill A. Jablonowski、L. Michelle Elliott

  DOI：10.1021/jo00114a009

  日期：1995.5
• (Z)- and (E)-.gamma.-silyloxy allylic stannanes. Highly syn selective reagents for SE' additions to aldehydes
  作者：James A. Marshall、Gregory S. Welmaker

  DOI：10.1021/jo00052a033

  日期：1992.12

  The (E)-gamma-silyloxy allylic stannane 2E, available in one step through addition of Bu(Bu3Sn)Cu(CN)Li2 to crotonaldehyde and subsequent in situ quenching of the enolate with t-BuMe2SiCl, undergoes BF3-promoted addition to representative aldehydes 3a-e, affording syn adducts 4a-e with >99:1 diastereoselectivity. The (Z)-gamma-silyloxy allylic stannane 2Z can be prepared by treatment of the adduct from Bu3SnLi and crotonaldehyde with TBSOTf in the presence of i-Pr2NEt. Stannane 2Z also affords syn adducts upon BF3-promoted addition to aldehydes 3a-e but with somewhat lower diastereoselectivity (93:7-99:1).