(+)-(2S,3S)-2,3-bis(benzyloxy)-4-((tert-butyldiphenylsilyl)oxy)butan-1-ol | 1217469-46-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(2S,3S)-2,3-bis(benzyloxy)-4-((tert-butyldiphenylsilyl)oxy)butan-1-ol
• 英文别名: (2S,3S)-2,3-Bis(benzyloxy)-4-{[tert-butyl(diphenyl)silyl]oxy}-1-butanol；(2S,3S)-4-[tert-butyl(diphenyl)silyl]oxy-2,3-bis(phenylmethoxy)butan-1-ol
• CAS: 1217469-46-9
• 化学式: C₃₄H₄₀O₄Si
• 分子量: 540.775
• InChiKey: XTYUEOBLEGSTSC-LQJZCPKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+)-(2S,3S)-2,3-bis(benzyloxy)-4-((tert-butyldiphenylsilyl)oxy)butan-1-ol 在 草酰氯 、 双(三甲基硅烷基)氨基钾 、 二甲基亚砜 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.25h， 生成 {[(2S,3S)-2,3-bis(benzyloxy)-5-methoxypent-4-en-1-yl]oxy}(tert-butyl)diphenylsilane
  参考文献：
  名称：

  A Stereoconvergent Intramolecular Diels–Alder Cycloaddition Related to the Construction of the Decalin Core of neo-Clerodane Diterpenoids

  摘要：

  Several examples of a highly specific, stereoconvergent intramolecular Diels-Alder cycloaddition that led to the trans-decalin core of neo-clerodane diterpenoids are described. The relative configuration adjacent to the dienophile, which led to C4 of the decalin system, as well as the electron withdrawing effects of various substituents and conformational rigidity of the Diels-Alder precursors were explored.

  DOI：

  10.1021/jo400029u
• 作为产物：
  描述：

  (2S,3S)-2,3-bis(benzyloxy)-4-(tert-butyldiphenylsilyloxy)-1-(3,4-dimethoxybenzyloxy)butane 在 [双(三氟乙酰氧基)碘]苯 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以96%的产率得到(+)-(2S,3S)-2,3-bis(benzyloxy)-4-((tert-butyldiphenylsilyl)oxy)butan-1-ol
  参考文献：
  名称：

  Effective chemoselective deprotection of 3,4-dimethoxybenzyl (3,4DMB) ethers in the presence of benzyl and p-methoxybenzyl (PMB) ethers by phenyliodine(III) bis(trifluoroacetate) (PIFA)

  摘要：

  In this Letter, a selective deprotection of the alcohol protecting 3,4-dimethoxybenzyl ((DMB)-D-3,4) group is described. The hypervalent iodine(III) reagent phenyliodine bis(trifluoroacetate) (PIFA) is found to be an efficient reagent for the chemoselective deprotection of (DMB)-D-3,4 ethers in the presence of benzyl, p-methoxybenzyl, methoxymethyl, tert-butyldimethylsilyl, and tert-butyldiphenylsilyl ethers under mild conditions. This is the first example of the selective deprotection of the (DMB)-D-3,4 group from a hydroxy group with PIFA. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.08.049

文献信息

• Investigation of Diastereoselective Acyclic α-Alkoxydithioacetal Substitutions Involving Thiacarbenium Intermediates
  作者：Michel Prévost、Starr Dostie、Marie-Ève Waltz、Yvan Guindon

  DOI：10.1021/jo502181a

  日期：2014.11.7

  Reported herein is an experimental and theoretical study that elucidates why silylated nucleobase additions to acyclic alpha-alkoxythiacarbenium intermediates proceed with high 1,2-syn stereocontrol (anti-Felkin-Anh), which is opposite to what would be expected with corresponding activated aldehydes. The acyclic thioaminals formed undergo intramolecular cyclizations to provide nucleoside analogues with anticancer and antiviral properties. The factors influencing the selectivity of the substitution reaction have been examined thoroughly. Halothioether species initially form, ionize in the presence (low dielectric media) or absence (higher dielectric media) of the nucleophile, and react through S(N)2-like transition structures (TS A and D), where the a-alkoxy group is gauche to the thioether moiety. An important, and perhaps counterintuitive, observation in this work was that calculations done in the gas phase or low dielectric media (toluene) are essential to locate the product- and rate-determining transition structures (C-N bond formation) that allow the most reasonable prediction of selectivity and isotope effects for more polar solvents (THF, MeCN). The triangle triangle G +/- (G(TSA)-(TSD)) obtained in silico are consistent with the preferential formation of 1,2-syn product and with the trends of stereocontrol displayed by 2,3-anti and 2,3-syn alpha,beta-bis-alkoxydithioacetals.
• Synthesis of 1′,2′-<i>cis</i>-Nucleoside Analogues: Evidence of Stereoelectronic Control for S_N2 Reactions at the Anomeric Center of Furanosides
  作者：Michel Prévost、Olivier St-Jean、Yvan Guindon

  DOI：10.1021/ja104429y

  日期：2010.9.8

  We are reporting a highly diastereoselective route to 1 ',2 '-cis-nucleoside analogues in the D-ribo, D-lyxo, D-xylo, and D-arabinoside series. Five-membered ring lactols undergo highly selective N-glycosidation reactions in the presence of dimethylboron bromide with different silylated nucleobases. Stereoelectronic control plays a crucial role for the observed induction, and the products are proposed to be formed through S(N)2 "exploded" transition states. This approach shows great potential considering its simplicity and selectivity for the synthesis of nucleoside analogues, an important class of molecules in medicinal chemistry.