(Z)-2,2,11,11-tetramethyl-3,3,10,10-tetraphenyl-4,9-dioxa-3,10-disiladodec-6-ene | 145365-08-8

• 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: (Z)-2,2,11,11-tetramethyl-3,3,10,10-tetraphenyl-4,9-dioxa-3,10-disiladodec-6-ene
• 英文别名: tert-butyl-[(Z)-4-[tert-butyl(diphenyl)silyl]oxybut-2-enoxy]-diphenylsilane
• CAS: 145365-08-8
• 化学式: C₃₆H₄₄O₂Si₂
• 分子量: 564.915
• InChiKey: XRLXSDRDWLDYBS-VXPUYCOJSA-N

物化性质

• 沸点：
  573.4±50.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  40.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (Z)-2,2,11,11-tetramethyl-3,3,10,10-tetraphenyl-4,9-dioxa-3,10-disiladodec-6-ene 在 二甲基硫 、 四氯化锡 、 二异丁基氢化铝 、 臭氧 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (+)-(2S,5R)-1-<2-<<(tert-butyldiphenylsilyl)oxy>methyl>-1,3-oxathiolan-5-yl>-cystosine
  参考文献：
  名称：

  Choi, Woo-Baeg; Wilson, Lawrence J.; Yeola, Suresh, Journal of the American Chemical Society, 1991, vol. 113, # 24, p. 9377 - 9379

  摘要：

  DOI：
• 作为产物：
  描述：

  顺式-1,2-二羟甲基乙烯 、 叔丁基二苯基氯硅烷 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以97%的产率得到(Z)-2,2,11,11-tetramethyl-3,3,10,10-tetraphenyl-4,9-dioxa-3,10-disiladodec-6-ene
  参考文献：
  名称：

  由4,5-未取代的2,3-二氢异恶唑合成带有4-羟基异恶唑烷部分的1,2,3-三唑

  摘要：

  从容易获得的4,5-未取代的2,3-二氢异恶唑开始，已经以非对映选择性的方式合成了带有3-羟甲基化的4-羟基异恶唑烷部分的新1,2,3-三唑。使用二羟基化或环氧化反应将羟基引入异恶唑烷环中。

  DOI：

  10.1002/ejoc.202000737

文献信息

• Second-Generation Synthesis of the Northern Fragment of Mandelalide A: Role of π-Stacking on Sharpless Dihydroxylation of <i>cis</i>-Enynes
  作者：Ankan Ghosh、Alexander C. Brueckner、Paul Ha-Yeon Cheong、Rich G. Carter

  DOI：10.1021/acs.joc.9b01153

  日期：2019.7.19

  asymmetric and diastereomeric dihydroxylation of cis-enynes is disclosed. The use of neighboring, electron-rich benzoate esters proved key to the success of this process. Density functional theory study suggests that the substrate benzoate ester group rigidifies the dihydroxylation transition states by forming a favorable π-stacking interaction in both Major-TS and Minor-TS. The energetic preference for

  公开了一种基于π-堆叠的方法的发展，该方法用于增加顺式炔烃的Sharpless不对称和非对映异构二羟基化中的立体选择性。事实证明，使用相邻的富含电子的苯甲酸酯是该方法成功的关键。密度泛函理论研究表明，底物苯甲酸酯基团通过在Major-TS和Minor-TS中形成良好的π堆积相互作用，从而使二羟基化过渡态硬化。发现对Major-TS的能量偏爱部分是因为烯烃取代基具有良好的日蚀构象，而与Minor-TS中不利的二等分构象相反。证明了其在曼荼罗A的C15–C24北部的第二代合成中的应用。
• Enantioselective Deuteration of β-Substituted α,β-Unsaturated Esters by Rhodium-1,2-Bis(2,5-diphenylphospholano)ethane
  作者：Sébastien Lethu、Hikaru Ano、Michio Murata、Shigeru Matsuoka

  DOI：10.1002/ejoc.201701400

  日期：2018.1.17

  An efficient asymmetric deuteration of β‐substituted α,β‐unsaturated esters was developed. To protect the carboxylate moiety and provide a direct read‐out of enantiomeric excess, substrates were derived from chiral methyl mandelate esters and subjected to catalytic deuteration with rhodium‐1,2‐bis(2,5‐diphenylphospholano)ethane. The reaction proceeded catalytically, and the mechanism was clearly illustrated

  开发了有效的β-取代的α，β-不饱和酯的不对称氘代。为了保护羧酸酯部分并直接读出对映体过量，底物衍生自手性扁桃酸甲酯，并用铑1,2-双（2,5-二苯基膦基）乙烷进行催化氘化。该反应催化进行，并且使用DFT优化的结构清楚地说明了机理。
• An unexpected reversal of stereochemistry in a modification of the rychnovsky cyanohydrin alkylation
  作者：Linda Joy Brzezinski、Dinah D. Levy、James W. Leahy

  DOI：10.1016/s0040-4039(00)78353-5

  日期：1994.10

  Alkylation of cyanohydrin 1,3-acetonides with unsaturated substitution at the 2-position is described. The stereochemistry of the products obtained from this reaction was opposite to that anticipated.

  描述了在2-位具有不饱和取代的氰醇1,3-丙酮化物的烷基化。从该反应获得的产物的立体化学与预期的相反。
• Gram-Scale Synthesis of (+)-Spongistatin 1: Development of An Improved, Scalable Synthesis of the F-Ring Subunit, Fragment Union, and Final Elaboration
  作者：Amos B. Smith、Takashi Tomioka、Christina A. Risatti、Jeffrey B. Sperry、Chris Sfouggatakis

  DOI：10.1021/ol801792k

  日期：2008.10.2

  In a quest to develop an effective, scalable synthesis of (+)-spongistatin 1 ( 1), we devised a concise, third-generation scalable synthesis of (+)- 7, the requisite F-ring tetrahydropyran aldehyde, employing a proline-catalyzed cross-aldol reaction. Subsequent elaboration to (+)-EF Wittig salt (+)- 3, followed by union with advanced ABCD aldehyde (-)- 4, macrolactonization and global deprotection

  为了开发一种有效、可规模化的 (+)-海绵抑素 1 (1) 合成方法，我们设计了一种简洁的第三代可规模化合成 (+)- 7，这是必需的 F 环四氢吡喃醛，采用脯氨酸-催化交叉羟醛反应。随后精制为 (+)-EF Wittig 盐 (+)- 3，然后与先进的 ABCD 醛 (-)- 4 结合、大环内酯化和整体脱保护，从而获得 >1.0 g 的全合成 (+)-海绵抑素 1 ( 1 ）。
• Total Synthesis of Tautomycin
  作者：Masato Oikawa、Tohru Ueno、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1021/jo00121a026

  日期：1995.8

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.