2-Allyl-4,4,5,5-tetramethyl-2-vinyloxy-[1,3,2]dioxasilolane | 467245-68-7

• 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-Allyl-4,4,5,5-tetramethyl-2-vinyloxy-[1,3,2]dioxasilolane
• 英文别名: 2-ethenoxy-4,4,5,5-tetramethyl-2-prop-2-enyl-1,3,2-dioxasilolane
• CAS: 467245-68-7
• 化学式: C₁₁H₂₀O₃Si
• 分子量: 228.363
• InChiKey: UGDXSQFIYSYLGG-UHFFFAOYSA-N

物化性质

• 沸点：
  197.9±33.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 2-Allyl-4,4,5,5-tetramethyl-2-vinyloxy-[1,3,2]dioxasilolane 以 甲苯 为溶剂， 反应 24.0h， 以60%的产率得到1-phenylhex-5-ene-1,3-diol
  参考文献：
  名称：

  Strained Silacycles in Organic Synthesis:  The Tandem Aldol−Allylation Reaction

  摘要：

  Allyl(crotyl)enolsilanes, when constrained in a five-membered ring with a 1,2-diol, react with aldehydes in a tandem aldol-allylation reaction to give polyketide fragments. These experimentally trivial and efficient reactions establish two new carbon-carbon bonds and up to four new stereocenters. The silane reagents, which owe their reactivity to strain release Lewis acidity, are easily prepared and stable to storage.

  DOI：

  10.1021/ja027655f
• 作为产物：
  描述：

  乙烯氧基三甲基硅烷 、 2-Allyl-2-chloro-4,4,5,5-tetramethyl-[1,3,2]dioxasilolane 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以70%的产率得到2-Allyl-4,4,5,5-tetramethyl-2-vinyloxy-[1,3,2]dioxasilolane
  参考文献：
  名称：

  Strained Silacycles in Organic Synthesis:  The Tandem Aldol−Allylation Reaction

  摘要：

  Allyl(crotyl)enolsilanes, when constrained in a five-membered ring with a 1,2-diol, react with aldehydes in a tandem aldol-allylation reaction to give polyketide fragments. These experimentally trivial and efficient reactions establish two new carbon-carbon bonds and up to four new stereocenters. The silane reagents, which owe their reactivity to strain release Lewis acidity, are easily prepared and stable to storage.

  DOI：

  10.1021/ja027655f

文献信息

• Reagents for asymmetric allylation, aldol, and tandem aldol and allylation reactions
  申请人：Leighton L. James

  公开号：US20050288525A1

  公开（公告）日：2005-12-29

  A new class of reagents and method of use of the reagents in the reaction of the reagents with electrophilic compounds. The invention in one embodiment is directed to a method for the formation of an alcohol of the formula (I). The method includes reacting reagent of the formula (II) with an aldehyde of the formula R 10 CHO to form the alcohol. X 3 is one of O and C(R 4 )(R 5 ). Each of X 1 and X 2 is independently O or N—R. Each of C a and C b is independently an achiral center, an (S) chiral center or an (R) chiral center. R a and R b are (i) each independently C 1-10 alkyl, C 6-10 aryl or C 3-9 heteroaryl, or (ii) taken together to form a C 3 -C 4 alkylene chain which together with C a and C b forms a 5-membered or 6-membered aliphatic ring. R c and R d are each independently hydrogen, C 1-10 alkyl, C 6-10 aryl or C 3-9 heteroaryl. R is C 1-10 alkyl, C 6-10 aryl or C 3-9 heteroaryl. Each of R 1 , R 2 , R 3 , R 4 , R 5 is independently hydrogen, C 1 -C 10 alkyl, C 6-10 aryl, C 3-9 heteroaryl, C 1-10 alkoxy, C 6-10 aryloxy, C 1-10 dialkylamino, C 1-10 alkyl-C 6-10 arylamino, C 1-10 diarylamino, or halogen. R 6 is halogen, hydrogen, C 1-10 alkyl, C 6-10 aryl, C 3-9 heteroaryl, C 1-10 alkoxy, C 6-10 aryloxy, C 1-10 alkyl-C 6-10 arylamino, C 1-10 diarylamino, OSO 2 CF 3 or SR. R 10 may be C 1-10 alkyl, C 6-10 aryl, or C 3-9 heteroaryl.

  一种新的试剂类别及其在与亲电性化合物反应中的使用方法。该发明在一种实施例中涉及一种制备式（I）的醇的方法。该方法包括将式（II）的试剂与式R10CHO的醛反应以形成醇。X3是O和C（R4）（R5）中的一个。X1和X2各自独立地是O或N-R。Ca和Cb各自是一个无手性中心，一个（S）手性中心或一个（R）手性中心。Ra和Rb是（i）各自独立的C1-10烷基，C6-10芳基或C3-9杂环芳基，或（ii）一起形成一个C3-C4烷基链，该链与Ca和Cb一起形成一个5-成员或6-成员脂环。Rc和Rd各自独立地为氢，C1-10烷基，C6-10芳基或C3-9杂环芳基。R为C1-10烷基，C6-10芳基或C3-9杂环芳基。R1、R2、R3、R4、R5各自独立地为氢，C1-C10烷基，C6-10芳基，C3-9杂环芳基，C1-10烷氧基，C6-10芳氧基，C1-10二烷基氨基，C1-10烷基-C6-10芳基氨基，C1-10二芳基氨基或卤素。R6为卤素，氢，C1-10烷基，C6-10芳基，C3-9杂环芳基，C1-10烷氧基，C6-10芳氧基，C1-10烷基-C6-10芳基氨基，C1-10二芳基氨基，OSO2CF3或SR。R10可以是C1-10烷基，C6-10芳基或C3-9杂环芳基。
• Reagents for asymmetric allylation, aldol, and tandem aldol and allyation reactions
  申请人：The Trustees of Columbia University In the City of New York

  公开号：US07534905B2

  公开（公告）日：2009-05-19

  A new class of reagents and method of use of the reagents in the reaction of the reagents with electrophilic compounds. The invention in one embodiment is directed to a method for the formation of an alcohol of the formula (I). The method includes reacting a reagent of the formula (II) with an aldehyde of the formula R10CHO to form the alcohol. X3 is one of O and C(R4)(R5). Each of X1 and X2 is independently O or N—R. Each of Ca and Cb is independently an achiral center, an (S) chiral center or an (R) chiral center. Ra and Rb are (i) each independently C1-10 alkyl, C6-10 aryl or C3-9 heteroaryl, or (ii) taken together to form a C3—C4 alkylene chain which together with Ca and Cb forms a 5-membered or 6-membered aliphatic ring. Rc and Rd are each independently hydrogen, C1-10 alkyl, C6-10 aryl or C3-9 heteroaryl. R is C1-10 alkyl, C6-10 aryl or C3-9 heteroaryl. Each of R1, R2, R3, R4, R5 is independently hydrogen, C1—C10 alkyl, C6-10 aryl, C3-9 heteroaryl, C1-10 alkoxy, C6-10 aryloxy, C1-10 dialkylamino, C1-10 alkyl-C6-10 arylamino, C1-10 diarylamino, or halogen. R6 is halogen, hydrogen, C1-10 alkyl, C6-10 aryl, C3-9 heteroaryl, C1-10 alkoxy, C6-10 aryloxy, C1-10 alkyl-C6-10 arylamino, C1-10 diarylamino, OSO2CF3 or SR. R10 may be C1-10 alkyl, C6-10 aryl, or C3-9 heteroaryl.

  一种新型试剂及其在试剂与亲电性化合物反应中的使用方法。该发明在一种实施例中是针对式(I)的醇形成方法。该方法包括将式(II)的试剂与式R10CHO的醛反应以形成醇。其中，X3为O和C(R4)(R5)中的一个。X1和X2各自独立地为O或N-R。Ca和Cb各自独立地为非手性中心、(S)手性中心或(R)手性中心。Ra和Rb为(i)各自独立地为C1-10烷基、C6-10芳基或C3-9杂环芳基，或(ii)一起形成C3-C4烷基链，该链与Ca和Cb一起形成5-或6-成员的脂环。Rc和Rd各自独立地为氢、C1-10烷基、C6-10芳基或C3-9杂环芳基。R为C1-10烷基、C6-10芳基或C3-9杂环芳基。R1、R2、R3、R4和R5各自独立地为氢、C1-C10烷基、C6-10芳基、C3-9杂环芳基、C1-10烷氧基、C6-10芳氧基、C1-10二烷基氨基、C1-10烷基-C6-10芳基氨基、C1-10二芳基氨基或卤素。R6为卤素、氢、C1-10烷基、C6-10芳基、C3-9杂环芳基、C1-10烷氧基、C6-10芳氧基、C1-10烷基-C6-10芳基氨基、C1-10二芳基氨基、OSO2CF3或SR。R10可以是C1-10烷基、C6-10芳基或C3-9杂环芳基。
• Strained Silacycles in Organic Synthesis:  The Tandem Aldol−Allylation Reaction
  作者：Xiaolun Wang、Qinglin Meng、Andrew J. Nation、James L. Leighton

  DOI：10.1021/ja027655f

  日期：2002.9.1

  Allyl(crotyl)enolsilanes, when constrained in a five-membered ring with a 1,2-diol, react with aldehydes in a tandem aldol-allylation reaction to give polyketide fragments. These experimentally trivial and efficient reactions establish two new carbon-carbon bonds and up to four new stereocenters. The silane reagents, which owe their reactivity to strain release Lewis acidity, are easily prepared and stable to storage.