(E,rel-4S,5R)-4-<(tert-butyldimethylsilyl)oxy>-2-undecen-5-ol | 135307-23-2

• 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,rel-4S,5R)-4-<(tert-butyldimethylsilyl)oxy>-2-undecen-5-ol
• 英文别名: (E)-(rel-4S,5R)-4-((tert-butyldimethylsilyl)oxy)-2-undecen-5-ol；(E)-(rel-4S,5R)-4-[(tert-butyldimethylsilyl)oxy]-2-undecen-5-ol；(E,4R,5S)-4-[tert-butyl(dimethyl)silyl]oxyundec-2-en-5-ol
• CAS: 135307-23-2；135327-63-8；145278-63-3
• 化学式: C₁₇H₃₆O₂Si
• 分子量: 300.557
• InChiKey: IZRRINXDOXYQBJ-FKZVYCBESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.28
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (E)-(rel-4R,5S)-4-((tert-butyldimethylsilyl)oxy)-5-(chloroacetoxy)-2-undecene 在 ammonium hydroxide 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以75%的产率得到(E,rel-4S,5R)-4-<(tert-butyldimethylsilyl)oxy>-2-undecen-5-ol
  参考文献：
  名称：

  (Z)- and (E)-.gamma.-silyloxy allylic stannanes. Highly syn selective reagents for SE' additions to aldehydes

  摘要：

  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).

  DOI：

  10.1021/jo00052a033

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。
• Solid-Support Synthesis of 1,2-Diols and <i>γ</i>-Lactones Through Addition of <i>α</i>-(Benzoyloxy)crotylindium Reagents to Aldehydes
  作者：Janine Cossy、Chrystelle Rasamison、Domingo Gomez Pardo、James A. Marshall

  DOI：10.1055/s-2001-13367

  日期：——

  A procedure for the solid phase synthesis of 1,2-diols and γ-lactones from α-(hydroxy)crotylstannane has been developed through transmetalation with InBr3. A variety of 1,2-diols and γ-lactones were synthesized in satisfactory yields and, in some cases, with excellent diastereoselectivity. The products are formed free of tin contamination.

  通过 InBr3 的金属转移，开发了从 α-（羟基）巴豆基锡烷固相合成 1,2-二醇和 γ-内酯的方法。各种1,2-二醇和γ-内酯的合成都具有令人满意的产率，并且在某些情况下具有优异的非对映选择性。产品不含锡污染。
• Chiral γ-silyloxy allylstannanes as synthetic reagents. Proof of absolute configuration
  作者：James A. Marshall、Gregory S. Welmaker

  DOI：10.1016/s0040-4039(00)71247-0

  日期：1991.5

  gamma-Silyloxy allylstannanes can be prepared directly from alpha-hydroxy allylstannanes by treatment with TBSOTf and (i-Pr)2NEt in CH2Cl2. The attendant 1,3-isomerization proceeds by an anti pathway as shown by comparison of the absolute configuration of reactant and product.