(4S,2E)-5-(tert-butyldiphenylsilyloxy)-2,4-dimethylpent-2-enal | 165258-10-6

• 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: (4S,2E)-5-(tert-butyldiphenylsilyloxy)-2,4-dimethylpent-2-enal
• 英文别名: (S,E)-5-[(tert-butyldiphenylsilyl)oxy]-2,4-dimethylpent-2-enal；(S,E)-2,4-dimethyl-5-(tert-butyldiphenylsilyloxy)pent-2-enal；(E,4S)-5-[tert-butyl(diphenyl)silyl]oxy-2,4-dimethylpent-2-enal
• CAS: 165258-10-6
• 化学式: C₂₃H₃₀O₂Si
• 分子量: 366.576
• InChiKey: KYMJZAYLXKYBCJ-UETJRYKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 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：

  (4S,2E)-5-(tert-butyldiphenylsilyloxy)-2,4-dimethylpent-2-enal 在 N-乙基哌啶 、 2,6-二甲基吡啶 、 sodium hydroxide 、 锂硼氢 、 tin(II) trifluoromethanesulfonate 、 三甲基铝 、 仲丁基锂 、 trityl tetrafluoroborate 、 二异丁基氢化铝 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 正庚烷 、 二氯甲烷 、 环己烷 、 水 、 甲苯 为溶剂， 反应 31.33h， 生成 (3R,4R,6S,7S,8E,10S)-6,10-bis[[tert-butyl(dimethyl)silyl]oxy]-3-methoxy-12-[(4-methoxyphenyl)methoxy]-7,9-dimethyldodeca-1,8-dien-4-ol
  参考文献：
  名称：

  Synthesis of the N-Acetylcysteamine Thioester of seco-Proansamitocin

  摘要：

  The enantioselective total synthesis of the N-acetylcysteamine thioester of seco-proansamitocin, a key biosynthetic intermediate of the highly potent antitumor agent ansamitocin, is described, which twice utilizes the Nagao acetate aldol reaction, as well as an indium-mediated alkynylation of a benzyl bromide followed by carboalumination. The key step is a Heck reaction between two terminal alkenes for merging the two major fragments.

  DOI：

  10.1021/ol052588q
• 作为产物：
  描述：

  (E,4S)-ethyl-5-(tert-butyldiphenylsilyloxy)-2,4-dimethyl-2-pentenoate 在 二异丁基氢化铝 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 (4S,2E)-5-(tert-butyldiphenylsilyloxy)-2,4-dimethylpent-2-enal
  参考文献：
  名称：

  Synthesis of the N-Acetylcysteamine Thioester of seco-Proansamitocin

  摘要：

  The enantioselective total synthesis of the N-acetylcysteamine thioester of seco-proansamitocin, a key biosynthetic intermediate of the highly potent antitumor agent ansamitocin, is described, which twice utilizes the Nagao acetate aldol reaction, as well as an indium-mediated alkynylation of a benzyl bromide followed by carboalumination. The key step is a Heck reaction between two terminal alkenes for merging the two major fragments.

  DOI：

  10.1021/ol052588q

文献信息

• 2‐Iodoxybenzoic Acid Tosylates: the Alternative to Dess–Martin Periodinane Oxidizing Reagents
  作者：Mekhman S. Yusubov、Pavel S. Postnikov、Roza Ya. Yusubova、Akira Yoshimura、Gerrit Jürjens、Andreas Kirschning、Viktor V. Zhdankin

  DOI：10.1002/adsc.201700776

  日期：2017.9.18

  Two powerful hypervalent iodine(V) oxidants, DMP‐OTs (1‐tosyloxy‐1,1‐diacetoxy‐1H‐1λ5‐benzo[d][1,2]iodoxol‐3‐one) and IBX‐OTs (1‐tosyloxy‐1‐oxo‐1H‐1λ5‐benzo[d][1,2]iodoxol‐3‐one) show high reactivity in the oxidation of structurally complex primary and secondary alcohols, which are highly functionalized polyketide or terpene fragments or steroids. The yields of the corresponding carbonyl compounds

  两个强大的高价碘（V）氧化剂，DMP-OTS（1-甲苯磺酰氧基-1,1-二乙酰氧基-1- ħ -1λ 5 -苯并[ d ] [1,2] iodoxol -3-酮）和IBX-OTS（1 -tosyloxy -1-氧代-1- ħ -1λ 5 -苯并[ d] [1,2] iodoxol-3-one）在结构复杂的伯醇和仲醇的氧化中显示出高反应活性，这些伯醇和仲醇是高度官能化的聚酮化合物或萜烯片段或类固醇。对于使用吡啶作为添加剂的方案，相应的羰基化合物的产率甚至更高。氧化在室温下进行非常迅速，保留了保护基和π系统，并提供了相应的羰基化合物，收率非常好。此外，IBX-OTs是一种有效的试剂，可用于甾族醇氧化脱氢为相应的烯酮。
• Stereocontrol in Asymmetric S_E′ Reactions of γ-Substituted α,β-Unsaturated Aldehydes
  作者：David R. Williams、Bruce A. Atwater、Seth A. Bawel、Pucheng Ke、Osvaldo Gutierrez、Dean J. Tantillo

  DOI：10.1021/ol403351x

  日期：2014.1.17

  Asymmetric SE′ reactions of (E)- and (Z)-γ-substituted-α,β-unsaturated aldehydes have been studied for the stereocontrolled preparation of nonracemic alcohols. Mild exchange reactions of allylic stannanes provide access to chiral 1,3-bis(tolylsulfonyl)-4,5-diphenyl-1,3-diaza-2-borolidines. These reagents display reactivity with the γ-substituted α,β-unsaturated aldehydes, which is characterized by

  已经研究了（E）-和（Z）-γ-取代的α，β-不饱和醛的不对称S E '反应，用于立体控制非外消旋醇的制备。烯丙基锡烷的温和交换反应可提供手性1,3-双（甲苯磺酰基）-4,5-二苯基-1,3-二氮杂-2-硼烷核苷。这些试剂与γ-取代的α，β-不饱和醛具有反应性，其特征在于立体控制的元素匹配和错配。计算分析（使用密度泛函理论）提供了宝贵的见识，可指导反应的发展。
• Progress towards the total synthesis of tedanolide: an efficient assembly of the C1–C11 subunit
  作者：Teck-Peng Loh、Li-Chun Feng

  DOI：10.1016/s0040-4039(01)01169-8

  日期：2001.8

  The C1–C11 subunit of tedanolide was constructed using a boron-mediated syn aldol reaction as the key step to control the C6 and C7 stereocenters. Other features of this work include the asymmetric Sharpless dihydroxylation to incorporate the C2, C3 hydroxyl groups, selective protection of the hydroxyl group at C2 as well as the usage of a tert-butyl ester to tolerate the attack of Grignard and enolate

  使用硼介导的顺式醇醛缩合反应作为控制C 6和C 7立体中心的关键步骤，构建了泰达内酯的C 1 -C 11亚基。这项工作的其他功能包括不对称二羟基化夏普勒斯掺入的C 2，C 3羟基基团，在C羟基的选择性保护2以及的使用一叔丁基酯容忍格利雅和烯醇化物试剂的攻击。
• Synthesis of the Naphthoquinone Nucleus of Awamycin
  作者：William R. Roush、D. Scott Coffey

  DOI：10.1021/jo00119a018

  日期：1995.7

  A synthesis of ketone 4, corresponding to the fully elaborated naphthoquinone nucleus of awamycin, is described. The synthesis involves the Diels-Alder reaction between diene 8 and quinone 9 to construct naphthoquinone 10, the coupling of bromide 15 and an ansa chain surrogate 17 via an aryllithium intermediate, and a late stage 1,4-addition of NaSMe to naphthoquinone 23 to afford the ketone 4.
• Synthesis of the <i>N</i>-Acetylcysteamine Thioester of <i>s</i><i>eco</i>-Proansamitocin
  作者：Thomas Frenzel、Marco Brünjes、Monika Quitschalle、Andreas Kirschning

  DOI：10.1021/ol052588q

  日期：2006.1.1

  The enantioselective total synthesis of the N-acetylcysteamine thioester of seco-proansamitocin, a key biosynthetic intermediate of the highly potent antitumor agent ansamitocin, is described, which twice utilizes the Nagao acetate aldol reaction, as well as an indium-mediated alkynylation of a benzyl bromide followed by carboalumination. The key step is a Heck reaction between two terminal alkenes for merging the two major fragments.