(2S,3S,4R)-1-(tert-butyldiphenylsilyloxy)-2,4-dimethyl-hex-5-en-3-ol | 106357-27-1

• 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: (2S,3S,4R)-1-(tert-butyldiphenylsilyloxy)-2,4-dimethyl-hex-5-en-3-ol
• 英文别名: (2S,3S,4R)-1-[tert-butyl(diphenyl)silyl]oxy-2,4-dimethylhex-5-en-3-ol
• CAS: 106357-27-1
• 化学式: C₂₄H₃₄O₂Si
• 分子量: 382.618
• InChiKey: VOTHQAIBUDKZGM-QTEQDKRBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.38
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S,4R)-1-(tert-butyldiphenylsilyloxy)-2,4-dimethyl-hex-5-en-3-ol 在 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 jones' reagent 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 为溶剂， 反应 10.5h， 生成 (2R,4R)-2,4-dimethyl-hex-5-enoic acid
  参考文献：
  名称：

  Total Synthesis of (−)-Spongidepsin

  摘要：

  A convergent and rapid stereoselective synthesis of (-)-spongidepsin has been achieved from the Roche ester in 14 steps with an overall yield of 13%.

  DOI：

  10.1021/ol061029w
• 作为产物：
  描述：

  (R)-3-(tert-butyldiphenylsilyloxy)-2-methylpropan-1-ol 在 草酰氯 、 4 A molecular sieve 、 二甲基亚砜 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 4.58h， 生成 (2S,3S,4R)-1-(tert-butyldiphenylsilyloxy)-2,4-dimethyl-hex-5-en-3-ol
  参考文献：
  名称：

  Roush, William R.; Palkowitz, Alan D.; Ando, Kaori, Journal of the American Chemical Society, 1990, vol. 112, # 17, p. 6348 - 6359

  摘要：

  DOI：

文献信息

• Diastereoselective Synthesis of Useful Building Blocks by Crotylation of β-Branched α-Methylaldehydes with Potassium Crotyltrifluoroborates
  作者：Kyosuke Tanaka、Yukiko Fujimori、Yoko Saikawa、Masaya Nakata

  DOI：10.1021/jo801106b

  日期：2008.8.1

  was realized by the substrate-controlled crotylation of β-branched α-methylaldehydes with potassium crotyltrifluoroborates. Especially, crotylation of 2-(1,3-dithian-2-yl)propanal with potassium (E)-crotyltrifluoroborate afforded, in good yield and with excellent diastereoselectivity, a useful building block that has different and potential functional groups on both ends.

  具有连续的甲基，羟基和甲基取代基的立体三单元组的非对映选择性结构是通过β-支化的α-甲基醛与巴豆基三氟硼酸钾的底物控制的丁酰化实现的。尤其是，用（E）-巴豆基三氟硼酸钾对2-（1,3-二苯-2-基）丙醛进行丁酰化，以高收率和优异的非对映选择性提供了有用的结构单元，该结构单元的两端具有不同的和潜在的官能团。
• Biochemistry‐Guided Prediction of the Absolute Configuration of Fungal Reduced Polyketides
  作者：Junya Takino、Akari Kotani、Taro Ozaki、Wenquan Peng、Jie Yu、Yian Guo、Susumu Mochizuki、Kazuya Akimitsu、Masaru Hashimoto、Tao Ye、Atsushi Minami、Hideaki Oikawa

  DOI：10.1002/anie.202110658

  日期：2021.10.18

  PK with multiple stereogenic centers. The absolute configurations of the stereogenic centers were determined by chemical degradation followed by comparison of the degradation products with synthetic standards. A stereochemical rule was proposed to explain the absolute configurations of other reduced PKs and highlights an error in the absolute configurations of a reported structure. The present work

  高度还原的聚酮化合物合酶 (HR-PKSs) 产生结构多样的聚酮化合物 (PKs)。PK 多样性由多种因素构成，包括 β-酮加工、链长、甲基化模式以及取代基的相对和绝对构型。我们检查了 PK 加工的立体化学过程，用于合成多羟基 PK，例如 phialotides、phomenoic 酸和 ACR 毒素。HR-PKS 基因、反式作用烯酰还原酶基因和截短的非核糖体肽合成酶基因的异源表达导致形成具有多个立体中心的线性 PK。立体中心的绝对构型通过化学降解确定，然后将降解产物与合成标准进行比较。提出了立体化学规则来解释其他还原 PK 的绝对构型，并突出报告结构的绝对构型中的错误。目前的工作表明，对功能相关的 HR-PKS 进行重点功能分析可以更好地理解立体化学过程。
• Electrochemical and photochemical approaches for the synthesis of the C28–C38 fragment of okadaic acid
  作者：Simon Dochain、Jean-Boris Nshimyumuremyi、Damien F. Dewez、Jean-François Body、Benjamin Elias、Michael L. Singleton、István E. Markó

  DOI：10.1016/j.tet.2019.02.060

  日期：2019.4

  probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core.

  冈田酸是蛋白磷酸酶1和2A（PP1和PP2A）的有效和选择性抑制剂，被广泛用作各种生化过程的探针。我们在这里描述了两种创新的方法，用于合成天然聚醚的末端C28-C38片段。Suárez的丙二酸酯的光化学氧化环化和丙二酸的电化学氧化已成功地用于关键螺环核心的组装。
• SYNTHESIS OF (S,S)-DIISOPROPYL TARTRATE (E)-CROTYLBORONATE AND ITS REACTION WITH ALDEHYDES: (2R,3R,4R)-1,2-DIDEOXY-2-ETHENYL-4,5-O-(1-METHYLETHYLIDENE)-XYLITOL
  作者：Sun, Huikai、Roush, William R.

  DOI：10.15227/orgsyn.088.0181

  日期：——
• Enantioselective and Diastereoselective Additions of Allylic Stannanes to Aldehydes Promoted by a Chiral (Acyloxy)borane Catalyst
  作者：James A. Marshall、Michael R. Palovich

  DOI：10.1021/jo980145c

  日期：1998.6.1

  A modified Yamamoto Lewis acid (CAB), prepared from the 2,6-dimethoxybenzoic ester of (R-R)-tartaric acid, and 1.5 equiv of BH3.THF was employed in additions of crotyltributyltin (6) and allyltributyltin (9) to representative achiral aldehydes in the presence of 2 equiv of (CF3CO)(2)O. The crotyltin additions proceeded with good to excellent diastereoselectivity and enantioselectivity affording the syn adducts 7a-e of 70-90% ee as major products (78:22-92:8). Addition of allylstannane 9 to cyclohexanecarboxaldehyde (1a) afforded the (R)-adduct of only 55% ee. In contrast, the use of Keck's BINOL catalyst gave 10, the allyl adduct of la, of 87% ee. However, addition of the crotylstannane to 1a with this catalyst led to a 65:35 mixture of syn and anti adducts 7a and 8a of 95% and 49% ee. Additions of crotylstannane 6 to (R)- and (S)-2-methyl-3-ODPS-propanal [(R)-11 and (S)-11] promoted by the modified CAB Lewis acid afforded the syn,syn and syn,anti products 12 and 14 in large predominance (98:2 and 90:10), indicative of effective complex control in the transition state. The results are consistent with the Corey H-bonded aldehyde transition-state proposal.