(S)-α-(Methoxymethoxy)crotyl tri-n-butylstannane | 84510-37-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: (S)-α-(Methoxymethoxy)crotyl tri-n-butylstannane
• 英文别名: [S-(E)]-tributyl[1-(methoxymethoxy)-2-butenyl]stannane；(S,E)-1-(methoxymethoxy)-1-tributylstannyl-2-butene；(1S,2E)-1-(tri-n-butylstannyl)-1-(methoxymethoxy)-2-butene；(E,S)-1-methoxymethoxy-2-butenyl tributylstannane；tributyl-[(E)-1-(methoxymethoxy)but-2-enyl]stannane
• CAS: 84510-37-2；131433-64-2；131433-65-3
• 化学式: C₁₈H₃₈O₂Sn
• 分子量: 405.209
• InChiKey: FVUIUPLNKMLNIA-PLJHVDPMSA-N

物化性质

• 沸点：
  382.1±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.94
• 重原子数：
  21
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-α-(Methoxymethoxy)crotyl tri-n-butylstannane 在 三(五氟苯基)硼烷 碳酸氢钠 作用下， 以 甲苯 为溶剂， 以66%的产率得到(S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene
  参考文献：
  名称：

  The BF3 and B(C6F5)3-catalyzed 1,3-isomerization of allylic stannanes

  摘要：

  A spectroscopic and chemical study of the stereospecific B(C6F5)(3)-catalyzed 1,3-isomerization of (E,S)-1-methoxymethoxy-2-butenyl tributylstannane to (Z,S)-1-methyl-3-methoxymethoxy-2-propenyl tributylstannane is described. A pathway involving an intermediate B(C6F5)(3) adduct is proposed based upon H-1- and Sn-119-NMR data. Analogous spectral evidence was not observed in the seemingly related BF3. OEt2-catalyzed isomerization. However, the similar product ratios obtained in B(C6F5)(3) and BF3. OEt2-promoted additions of the latter stannane to o- and p-methoxybenzaldehyde reveals a close similarity between the two and prompts speculation that the BF3. OEt2-catalyzed 1,3-isomerization proceeds by an analogous pathway. A pathway for the B(C6F5)(3)-promoted addition of allylic stannanes to o-methoxybenzaldehyde is also presented. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00642-8
• 作为产物：
  描述：

  三丁基锡锂 在 lithium aluminium tetrahydride 、 乙醇 、 (R)-1,1'-Bi-2-naphthol 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 22.5h， 生成 (S)-α-(Methoxymethoxy)crotyl tri-n-butylstannane
  参考文献：
  名称：

  SYNTHESIS OF (S,E)-1-(METHOXYMETHOXY)-1-TRIBUTYLSTANNYL-2-BUTENE

  摘要：

  DOI：

  10.15227/orgsyn.077.0098

文献信息

• Synthesis of Chiral α,δ-Dioxygenated Allylic Stannanes as Reagents for Carbohydrate Synthesis and Homologation
  作者：James A. Marshall、Albert W. Garofalo

  DOI：10.1021/jo961671b

  日期：1996.1.1

  delta-oxygenated allylic stannanes 4.4 and 4.5, prepared through addition of Bu(3)SnLi to gamma-OTBS crotonaldehyde 4.3c followed by etherification of the adduct with TBS-Cl or MOM-Cl, undergo transmetalation with InCl(3) and in situ addition to aldehydes leading to mainly anti adducts 5.1 or 5.2, accompanied by varying amounts of syn diastereomers. Selectivities of >95:5 can be realized with the MOM reagent 4.5

  通过将Bu（3）SnLi添加到γ-OTBS巴豆醛4.3c中，然后将加合物与TBS-Cl或MOM-Cl醚化制得的δ-加氧烯丙基锡烷4.4和4.5，然后与InCl（3）进行重金属化，然后在在醛中进行原位添加，主要生成抗加合物5.1或5.2，并伴有不同数量的顺式非对映异构体。使用MOM试剂4.5和ynals 4.3d和4.3e或环己烷甲醛4.3a可以实现> 95：5的选择性。用烯醛4.3b和4.3c，形成80∶20的反加合物和顺加合物的混合物。还已经制备了锡烷4.5的S对映体10.1作为碳水化合物合成的试剂。因此，在InCl（3）存在下向α-ODPS乙醛10.2中加成，使加成物10.3成为反对映体和顺式非对映异构体不可分离的90:10混合物。
• Three-Component Synthesis of Homoallylic Amines Promoted by Carboxylic Acids
  作者：Gang Zhao、Gui-long Li

  DOI：10.1055/s-2006-942548

  日期：——

  A highly selective, three-component reaction promoted by carboxylic acids for the synthesis of homoallylic amines has been developed. By using maleic acid or trifluoroacetic acid as a promoter, the reaction between a variety of aldehydes, aromatic amines, and allyltin reagents proceeds smoothly to afford the corresponding homoallylic amines in moderate to quantitative yields under mild conditions.

  已经开发了一种由羧酸促进的用于合成高烯丙基胺的高选择性三组分反应。通过使用马来酸或三氟乙酸作为促进剂，多种醛、芳香胺和烯丙基锡试剂之间的反应顺利进行，在温和条件下以中等至定量的产率得到相应的高烯丙基胺。
• Highly stereoselective synthesis of vicinal diols by stannous chloride-mediated addition of hydroxyallylic stannanes to aldehydes
  作者：Makoto Yasuda、Tatsuya Azuma、Kensuke Tsuruwa、Srinivasarao Arulananda Babu、Akio Baba

  DOI：10.1016/j.tetlet.2009.01.137

  日期：2009.7

  A new protocol for the synthesis of vicinal diols was accomplished by the reaction of unprotected α-hydroxymethylmetals, as hydroxymethyl anion equivalents, with aldehydes. The treatment of hydroxyallylic stannanes, which were prepared from α,β-unsaturated aldehydes and Bu3SnLi in situ, with various aldehydes gave but-3-en-1,2-diols in the presence of SnCl2. The stereochemistry of the diol and olefin

  通过未保护的α-羟甲基金属（如羟甲基阴离子当量）与醛的反应，完成了邻位二醇合成的新方案。由α，β-不饱和醛和Bu 3 SnLi原位制备的羟基锡烷与各种醛的处理在SnCl 2存在的情况下可生成3-en-1,2-二醇。二醇和烯烃部分的立体化学分别显示出顺-和E-选择性。我们提出以下反应机制；SnCl 2对羟基烯丙基锡进行金属重金属化产生重排的烯丙基锡（II）物种，该物种通过环状过渡态进行醛加成反应。未保护的羟基部分与锡（II）中心之间的严格相互作用说明了选择性。
• On the use of E-1-methoxymethoxybut-2-enyl(tri-n-butyl)stannane as a threo-selective, homo-enolate equivalent
  作者：Andrew J. Pratt、Eric J. Thomas

  DOI：10.1039/c39820001115

  日期：——

  (E)-1-Methoxymethoxybut-2-enyl(tri-n-butyl)stannane, readily available by addition of tri-n-butylstannyllithium to crotonaldehyde, and protection of the alcohol so formed using chloromethyl methyl ether, reacts on heating with aromatic and aliphatic aldehydes to give threo-4,5-disubstituted butyrolactones.

  （E）-1-甲氧基甲氧基丁-2-烯基（三正丁基）锡烷，可通过将三正丁基锡锂加到巴豆醛中而容易获得，并用氯甲基甲基醚保护如此形成的醇，在加热下与芳族化合物反应和脂族醛得到苏--4，5-二取代丁内酯。
• Marshall, James A.; Welmaker, Gregory S.; Gung, Benjamin W., Journal of the American Chemical Society, 1991, vol. 113, # 2, p. 647 - 656
  作者：Marshall, James A.、Welmaker, Gregory S.、Gung, Benjamin W.

  DOI：——

  日期：——