(E)-4-(t-butyldiphenylsilyl)oxy-2-butenal | 131380-48-8

• 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: (E)-4-(t-butyldiphenylsilyl)oxy-2-butenal
• 英文别名: (E)-4-((tert-butyldiphenylsilyl)oxy)but-2-enal；4-(tert-butyl-diphenyl-silanyloxy)-but-2-enal；(E)-4-[tert-butyl(diphenyl)silyl]oxybut-2-enal
• CAS: 131380-48-8
• 化学式: C₂₀H₂₄O₂Si
• 分子量: 324.495
• InChiKey: MGGIIAUQPJPLFZ-ZHACJKMWSA-N

物化性质

• 熔点：
  80-84 °C
• 沸点：
  404.9±45.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.32
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-4-(t-butyldiphenylsilyl)oxy-2-butenal 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二乙酯 、 4 A molecular sieve 、 Celite 、 sodium acetate 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 2.42h， 生成 (-)-lyxo-(4S,5S,6S)-7-(tert-butyldiphenylsiloxy)-5,6-epoxyhept-1-en-4-ol
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053
• 作为产物：
  描述：

  (E)-4-(tert-butyldiphenylsilyloxy)-2-buten-1-ol 在 manganese(IV) oxide 、 氧气 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以84%的产率得到(E)-4-(t-butyldiphenylsilyl)oxy-2-butenal
  参考文献：
  名称：

  分子内钯催化的亚甲基环丙烷的[3 + 2]环加成反应的立体化学方面

  摘要：

  描述了一系列包含立体化学定义的2,3-二取代的亚甲基环丙烷3或丙烯酸酯受体12-15的底物的制备和分子内钯催化的[3 + 2]环加成反应。提出的证据支持以下假设：这些环加成反应通过钯-三亚甲基甲烷类中间体进行，并且两个碳-碳键以高度异步的方式形成。

  DOI：

  10.1016/0040-4020(96)00160-3

文献信息

• Enantioselective preparation of C2-symmetrical 1,4-diols
  作者：Stephan Vettel、Paul Knochel

  DOI：10.1016/s0040-4039(00)78200-1

  日期：1994.8

  addition of functionalized dialkylzincs to the γ-alkoxyaldehydes 5, 6 and 7 provides 1,4-diols 1–3 with 73–99 %ee. After a simple reaction sequence, these diols are converted to chiral γ-alkoxyaldehydes which undergo a second catalytic enantioselective addition of the same diorganozinc providing C2-symmetrical 1,4-diols 10a–f with excellent diastereoselectivity (up to 97 : 3).

  在γ-烷氧基醛5、6和7上催化官能化的二烷基锌的催化对映选择性加成后，得到1,4-二醇1-3，其ee值为73-99。经过简单的反应序列后，这些二醇被转化为手性的γ-烷氧基醛，对第二种有机锌进行了第二次催化对映选择性加成，从而提供了具有出色的非对映选择性（高达97：3）的C 2对称的1,4-二醇10a-f。
• Switchable Synthesis of <i>Z</i> -Homoallylic Boronates and <i>E</i> -Allylic Boronates by Enantioselective Copper-Catalyzed 1,6-Boration
  作者：Yunfei Luo、Steven M. Wales、Stamatis E. Korkis、Iain D. Roy、William Lewis、Hon Wai Lam

  DOI：10.1002/chem.201801804

  日期：2018.6.12

  The enantioselective Cu‐catalyzed 1,6‐boration of (E,E)‐α,β,γ,δ‐unsaturated ketones is described, which gives homoallylic boronates with high enantiomeric purity and unexpectedly high Z‐selectivity. By changing the solvent, the outcome can be altered to give E‐allylic boronates.

  描述了（E，E）-α，β，γ，δ-不饱和酮的对映选择性Cu催化的1,6-硼酸酯，它使对映体硼酸酯具有高对映体纯度和出乎意料的高Z选择性。通过改变溶剂，可以改变结果，得到E-烯丙基硼酸盐。
• Copper(I)-Catalyzed Enantioselective 1,6-Borylation of α,β,γ,δ-Unsaturated Phosphonates
  作者：Hyesu Lee、Jaesook Yun

  DOI：10.1021/acs.orglett.8b03532

  日期：2018.12.21

  Copper(I)-catalyzed asymmetric 1,6-borylation of 1,3-dienylphosphonates was achieved using (S,S)-Ph-BPE as a chiral ligand. Regio-, stereo-, and enantioselective borylation successfully proceeded to afford phosphonate-containing allylboronates, with high enantioselectivity up to 97% ee. Further applications of the resulting products generated a valuable phosphonate analogue of γ-butyrolactone.

  使用（S，S）-Ph-BPE作为手性配体，得到铜（I）催化的1，3-二烯基膦酸酯的不对称1，6-硼酸酯化。区域，立体和对映体选择性硼化成功地进行，得到了含膦酸酯的烯丙基硼酸酯，具有高达97％ee的高对映体选择性。所得产物的进一步应用产生了有价值的γ-丁内酯的膦酸酯类似物。
• A Cycloaddition Cascade Approach to the Total Synthesis of (−)-FR182877
  作者：David A. Evans、Jeremy T. Starr

  DOI：10.1021/ja037643+

  日期：2003.11.1

  entire structure was established using two (4R)-4-benzyl-2-oxazolidinone-mediated boron aldol reactions. A 19-membered macrocarbocycle was synthesized by the coupling of two fragments using a regioselective Suzuki coupling (17 + 23 --> 26; 84%) and macrocyclization of a beta-keto ester (30 --> 31; 77%). Oxidation of 31 triggered a sequence of stereoselective transannular Diels-Alder reactions (32 -->34;

  已实现细胞毒性天然产物 (-)-FR182877 (1) 的不对称合成。使用两个 (4R)-4-benzyl-2-oxazolidinone 介导的硼醛醇反应建立了整个结构的手性。通过使用区域选择性 Suzuki 偶联 (17 + 23 --> 26; 84%) 和 β-酮酯的大环化 (30 --> 31; 77%) 偶联两个片段来合成 19 元大碳环。31 的氧化触发了一系列立体选择性跨环 Diels-Alder 反应（32 --> 34；63%），在关键的构建事件中形成了四个新环和七个新立体中心。该五环中间体随后转化为 (-)-FR182877。对跨环 Diels-Alder 环加成级联进行了半经验计算，以确定不对称诱导的起源。
• Total synthesis of the polyene macrolide antibiotic roxaticin. II. Total synthesis of roxaticin
  作者：Yuji Mori、Motoya Asai、Jun-ichiro Kawade、Hiroshi Furukawa

  DOI：10.1016/0040-4020(95)00215-t

  日期：1995.5

  Roxaticin has been synthesized in a convergent manner from the polyol segment 2, which was prepared by the Julia coupling reaction of sulfone 4 and aldehyde 8, and the polyene phosphonate 3. The cyclization was achieved by macrolactonization.

  罗沙汀是由多元醇链段2聚合合成的，多元醇链段2是通过砜4和醛8的朱莉娅偶联反应和多烯膦酸酯3制备的。通过大内酯化实现环化。