(S)-1-(tert-butyldiphenylsiloxy)-4-hydroxyhept-6-ene | 127793-68-4

• 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: (S)-1-(tert-butyldiphenylsiloxy)-4-hydroxyhept-6-ene
• 英文别名: (S)-7-(tert-butyldiphenylsilanyloxy)hept-1-en-4-ol；(S)-1-tert-Butyldiphenylsilyloxyhept-6-en-4-ol；(4S)-7-(tret-butyldiphenylsilyloxy)hept-1-en-4-ol；(4S)-1-(tert-butyldiphenylsilyloxy)hept-6-en-4-ol；(4S)-7-(tert-butyldiphenylsilyloxy)-hept-1-en-4-ol；(S)-7-(tert-butyldiphenylsilyloxy)hept-1-en-4-ol；(4S)-7-[tert-butyl(diphenyl)silyl]oxyhept-1-en-4-ol
• CAS: 127793-68-4
• 化学式: C₂₃H₃₂O₂Si
• 分子量: 368.591
• InChiKey: UCTJBDLSKNKLAS-HXUWFJFHSA-N

物化性质

• 沸点：
  443.7±45.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  (S)-1-(tert-butyldiphenylsiloxy)-4-hydroxyhept-6-ene 在 sodium tetrahydroborate 、 偶氮二甲酸二异丙酯 、 四丁基氟化铵 、 甲基磺酰氯 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (R)-3-(1-Hydroxyhept-6-en-4-yl)-2,3-dihydrooxazol-2-one
  参考文献：
  名称：

  Diastereoselective synthesis of 2,5-disubstituted 3-hydroxypyrrolidine and 2,6-disubstituted 3-hydroxypiperidine derivatives by radical cyclisation; synthesis of (+)-bulgecinine and (–)-desoxoprosopinine

  摘要：

  Cyclisation of the O-stannyl ketyl, generated from the aldehyde 17 by reaction with tributyltin hydride in the presence of AIBN, gives the 5-benzyloxymethyl-7-hydroxypyrrolooxazolidin as a diastereoisomeric mixture of 7 alpha-ol 18 and 7 beta-ol 19 (2: 1), with high diastereoselectivity with respect to the 5,7a positions, (+)-Bulgecinine 8 is enantioselectively synthesised by stereospecific reduction of the ketone 20, derived from compounds 18 and 19. In a similar way, cyclisation of compound 40 gives a 2: 1 mixture of compounds 41 and 42. Conversion of compound 41 into (-)-desoxoprosopinine 9 is successfully achieved.

  DOI：

  10.1039/p19960000793
• 作为产物：
  描述：

  3-[(4S)-2,2-二甲基-1,3-二氧戊烷-4-基]-丙醇 在 吡啶 、 4-二甲氨基吡啶 、 18-冠醚-6 、 三氟化硼乙醚 、 sodium hydride 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 50.67h， 生成 (S)-1-(tert-butyldiphenylsiloxy)-4-hydroxyhept-6-ene
  参考文献：
  名称：

  Diastereoselective synthesis of 2,5-disubstituted 3-hydroxypyrrolidine and 2,6-disubstituted 3-hydroxypiperidine derivatives by radical cyclisation; synthesis of (+)-bulgecinine and (–)-desoxoprosopinine

  摘要：

  Cyclisation of the O-stannyl ketyl, generated from the aldehyde 17 by reaction with tributyltin hydride in the presence of AIBN, gives the 5-benzyloxymethyl-7-hydroxypyrrolooxazolidin as a diastereoisomeric mixture of 7 alpha-ol 18 and 7 beta-ol 19 (2: 1), with high diastereoselectivity with respect to the 5,7a positions, (+)-Bulgecinine 8 is enantioselectively synthesised by stereospecific reduction of the ketone 20, derived from compounds 18 and 19. In a similar way, cyclisation of compound 40 gives a 2: 1 mixture of compounds 41 and 42. Conversion of compound 41 into (-)-desoxoprosopinine 9 is successfully achieved.

  DOI：

  10.1039/p19960000793

文献信息

• Fe/Cr- and Co/Cr-Mediated Catalytic Asymmetric 2-Haloallylations of Aldehydes
  作者：Michio Kurosu、Mei-Huey Lin、Yoshito Kishi

  DOI：10.1021/ja045557j

  日期：2004.10.1

  is reported. The coupling reaction is effected by the use of a chiral sulfonamide-Cr complex (prepared in situ from 1d, CrBr3, Fe(III) or from Co(II), Et3N, and Mn), TMSCl, and 2,6-lutidine. The method reported here is operationally simple and scalable, furnishing 3-halohomoallylic alcohols with a synthetically useful level of enantiomeric excess.

  报告了以催化不对称方式将醛和 3-bromo-2-halopropenes 偶联的第一个例子。偶联反应通过使用手性磺酰胺-Cr 络合物（由 1d、CrBr3、Fe(III) 或 Co(II)、Et3N 和 Mn 原位制备）、TMSCl 和 2,6-二甲基吡啶进行。此处报告的方法操作简单且可扩展，提供具有合成有用水平的对映体过量的 3-卤代烯丙醇。
• Catalytic Enantioselective Allyl- and Crotylboration of Aldehydes Using Chiral Diol•SnCl₄ Complexes. Optimization, Substrate Scope and Mechanistic Investigations
  作者：Vivek Rauniyar、Huimin Zhai、Dennis G. Hall

  DOI：10.1021/ja8016076

  日期：2008.7.1

  induction in the allylboration of aldehydes by commercially available allylboronic acid pinacol ester 1a. The corresponding homoallylic alcohol products of synthetically useful aliphatic aldehydes are obtained in excellent yields with up to 98:2 er. This combined acid manifold is also efficient in catalyzing the diastereo- and enantioselective crotylboration of aldehydes, thus providing the propionate

  我们报告了一类新的 C2 对称手性二醇，其源自对苯二酚骨架。在 Yamamoto 的路易斯酸辅助布朗斯台德酸度（LBA 催化）概念下，这些二醇与 SnCl 4 的组合导致可商购的烯丙基硼酸频哪醇酯 1a 在醛的烯丙基硼化中产生高水平的不对称诱导。合成有用的脂肪醛的相应高烯丙醇产品以高达 98:2 的产率获得。这种组合的酸歧管还可有效催化醛的非对映选择性和对映选择性巴豆基硼化反应，从而提供 >95:5 dr 和高达 98:2 er 的丙酸酯单元。最佳二醇 x SnCl4 配合物 Vivol (4m) x SnCl4 的 X 射线晶体结构，明确显示了这种 LBA 催化剂的 Brønsted 酸性特征及其高度不对称的环境。进一步的控制排除了可能的硼与手性二醇的酯交换机制，并指出频哪醇烯丙基硼酸酯 1 的 LBA 催化剂衍生的活化。由于二醇 x SnCl4 复合物的缓慢解离，需要少量过量的二醇为了抑制由游离
• Tandem Three‐Component Synthesis of <i>syn</i> ‐1,2‐ and <i>syn</i> ‐1,3‐Diol Derivatives
  作者：Keisuke Murata、Hiroya Takeshita、Keita Sakamoto、Haruhiko Fuwa

  DOI：10.1002/asia.201901660

  日期：2020.3.16

  development of efficient methods for stereocontrolled synthesis of polyol derivatives has been of continuing interest for the synthetic community. We describe herein tandem olefin cross-metathesis/hemiacetalization/intramolecular oxa-Michael addition of allylic/homoallylic alcohols, α,β-unsaturated ketones, and aldehydes, which enabled the synthesis of syn-1,2- and syn-1,3-diol derivatives in a step-economical

  对于多元醇衍生物的立体控制合成的有效方法的开发一直是合成界关注的焦点。我们在本文中描述了烯丙基/均烯丙基醇，α，β-不饱和酮和醛的串联烯烃交叉复分解/半缩醛化/分子内氧杂-Michael加成反应，从而能够合成syn-1,2-和syn-1,3-以分步经济的方式生产二醇衍生物。在随后的转化中，可以通过串联反应产物的乙缩醛部分的化学选择性/区域选择性裂解获得一系列差异保护的多元醇衍生物。
• Synthesis and assignment of the absolute configuration of the anti-Helicobacter pylori agents CJ-12,954 and CJ-13,014
  作者：Margaret A. Brimble、Christina J. Bryant

  DOI：10.1039/b709932k

  日期：——

  The synthesis of the spiroacetal-containing anti-Helicobacter pylori agents (3S,2″S,5″S,7″S)-1a (ent-CJ-12,954) and (3S,2″S,5″R,7″S)-2a (ent-CJ-13,014) has been carried out based on the convergent union of a 1 : 1 mixture of heterocycle-activated spiroacetal sulfones6 and 7 with (3S)-phthalide aldehyde5a. The synthesis of the (3R)-diastereomers (3R,2″S,5″S,7″S)-1b and (3R,2″S,5″R,7″S)-2b was also undertaken in a similar manner by union of (3R)-phthalide aldehyde5b with a 1 : 1 mixture of spiroacetal sulfones6 and 7. Comparison of the 1H and 13C NMR data, optical rotations and HPLC retention times of the synthetic compounds (3S,2″S,5″S,7″S)-1a and (3S,2″S,5″R,7″S)-2a and the (3R)-diastereomers (3R,2″S,5″S,7″S)-1b and (3R,2″S,5″R,7″S)-2b, with the naturally occurring compounds, established that the synthetic isomers 1a and 2a were in fact enantiomeric to the natural products CJ-12,954 and CJ-13,014. The (2S,8S)-stereochemistry in protected dihydroxyketone 21, the precursor to the mixture of spiroacetal sulfones6 and 7 was established via union of readily available (S)-acetylene 18 with aldehyde17 in which the (4S)-stereochemistry was established via asymmetric allylation. Deprotection and cyclization of protected dihydroxyketone 21 afforded an inseparable 1 : 1 mixture of spiroacetal alcohols24 and 25 that were converted into a 1 : 1 inseparable mixture of spiroacetal sulfones6 and 7. Phthalide-aldehyde 3a was prepared via intramolecular acylation of bromocarbamate 11 in which the (3S)-stereochemistry was established via asymmetric CBS reduction of ketone8.

  含螺缩醛的抗幽门螺旋杆菌药物(3S,2″S,5″S,7″S)-1a (ent-CJ-12,954)和(3S,2″S,5″R,7″S)-2a (ent-CJ-13,014)的合成是基于杂环激活的螺缩醛砜6和7与(3S)-邻苯二甲醛5a的1:1混合物的会聚结合。(3R)-非对映异构体(3R,2″S,5″S,7″S)-1b 和(3R,2″S,5″R,7″S)-2b 的合成也以类似的方法进行，即(3R)-邻苯二甲醛 5b 与螺醛类砜 6 和 7 的 1 : 1 混合物结合。比较了合成化合物（3S,2″S,5″S,7″S）-1a 和（3S,2″S,5″R,7″S）-2a 以及（3R）-非对映异构体（3R,2″S,5″S、7″S）-1b 和 (3R,2″S,5″R,7″S)-2b，确定合成异构体 1a 和 2a 事实上是天然产物 CJ-12,954 和 CJ-13,014 的对映体。受保护的二羟基酮 21（螺醛砜混合物 6 和 7 的前体）中的(2S,8S)-立体化学是通过现成的(S)-乙炔 18 与醛 17 结合而建立的，其中的(4S)-立体化学是通过不对称烯丙基化建立的。对受保护的二羟基酮 21 进行脱保护和环化，可得到 1 : 1 不可分离的螺醛醇混合物24 和 25，并将其转化为 1 : 1 不可分离的螺醛砜混合物6 和 7。酞醛 3a 是通过溴代氨基甲酸酯 11 的分子内酰化反应制备的，其中的 (3S)- 立体化学结构是通过酮的不对称 CBS 还原8 建立的。
• Total Synthesis of 13-Demethyllyngbyaloside B
  作者：Haruhiko Fuwa、Naoya Yamagata、Asami Saito、Makoto Sasaki

  DOI：10.1021/ol400408w

  日期：2013.4.5

  achieved. The 14-membered macrocyclic backbone was constructed in a convergent manner via esterification and ring-closing metathesis. The bromodiene side chain was introduced by means of a Stille-type reaction and a subsequent bromodesilylation. Finally, the rhamnopyranose unit was stereoselectively introduced by glycosylation under Schmidt conditions.

  已经实现了13-去甲基lyngbyaloside B的全合成，这是海洋大环内酯糖苷lyngbyaloside B的非天然类似物。通过酯化和闭环复分解以聚合方式构建14元大环骨架。通过Stille型反应和随后的溴代甲硅烷基化引入溴代二烯侧链。最后，在Schmidt条件下通过糖基化立体选择性地引入鼠李糖吡喃糖单元。