2-((tert-butyldimethylsilyloxy)methyl)pent-4-yn-1-ol | 1412889-81-6

• 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: 2-((tert-butyldimethylsilyloxy)methyl)pent-4-yn-1-ol
• 英文别名: 2-[[Tert-butyl(dimethyl)silyl]oxymethyl]pent-4-yn-1-ol；2-[[tert-butyl(dimethyl)silyl]oxymethyl]pent-4-yn-1-ol
• CAS: 1412889-81-6
• 化学式: C₁₂H₂₄O₂Si
• 分子量: 228.407
• InChiKey: NNZHMQBRSCSRRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2-((tert-butyldimethylsilyloxy)methyl)pent-4-yn-1-ol 在 1,3-丙二硫醇 、 4-二甲氨基吡啶 、 copper(l) iodide 、 2,6-二叔丁基-4-甲基吡啶 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 、 Zn(N₃)₂*Py₂ 、 trans-bis(triphenylphosphine)palladium dichloride 、 1,2-二溴四氯乙烷 、 偶氮二甲酸二异丙酯 、 camphor-10-sulfonic acid 、 sodium perchlorate 、 四丁基氟化铵 、 三氧化硫吡啶 、 copper(II) acetate monohydrate 、 戴斯-马丁氧化剂 、 silver nitrate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 三苯基膦 、 N,N'-二异丙基碳二亚胺 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氘代甲醇-d 、 水 、 二甲基亚砜 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， 反应 111.16h， 生成 (9R,10S)-8-deshydroxyajudazol A
  参考文献：
  名称：

  Total Synthesis of the Proposed Structure of 8-Deshydroxyajudazol A: A Modified Approach to 2,4-Disubstituted Oxazoles

  摘要：

  The total synthesis of the proposed structure for the minor Myxobacterial metabolite 8-deshydroxyajudazol A (3) is described. The isochromanone moiety present in the eastern fragment was constructed by an intramolecular-Diels-Alder (IMDA). Difficulties were encountered with the formation of the 2,4-disubstituted oxazole, so this was synthesized via a modified approach. This involved selective acylation of the diol 7 with acid 8, azide displacement of the secondary alcohol, and subsequent azide reduction in the presence of base which induced an O,N shift to give the hydroxyamide 23. Cyclodehydration then gave the desired oxazole 24 and deprotection followed by mesylation and elimination produced the C15 alkene S. Sonogashira coupling with the eastern fragment vinyl iodide 6 and partial reduction yielded 8-deshydroxyajudazol A (3).

  DOI：

  10.1021/jo302055w
• 作为产物：
  描述：

  炔丙基丙二酸二甲酯 在 咪唑 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 40.0h， 生成 2-((tert-butyldimethylsilyloxy)methyl)pent-4-yn-1-ol
  参考文献：
  名称：

  烯醇的非对映选择性钯催化的氧化级联羰基碳环化。

  摘要：

  开发了钯催化烯醇的氧化级联羰基碳环化反应。在温和的反应条件下，以高收率和高非对映选择性获得了一系列具有1,3-二烯基序的顺式[5,5]双环γ-内酯和γ-内酰胺。所获得的内酯/内酰胺产物是用于与N-苯基马来酰亚胺进行立体选择性Diels-Alder反应的可行底物，从而提供了具有更高分子复杂性的多环化合物。

  DOI：

  10.1021/acs.orglett.9b04134

文献信息

• Synthesis of 5-Iodo-1,2,3,4-tetrahydropyridines by Rhodium-Catalyzed Tandem Nucleophilic Attacks Involving 1-Sulfonyl-1,2,3-triazoles and Iodides
  作者：Zengming Man、Haican Dai、Yinping Shi、Dongdong Yang、Chuan-Ying Li

  DOI：10.1021/acs.orglett.6b02428

  日期：2016.10.7

  Sodium iodide is used for the first time as a nucleophile to trap an α-imino rhodium carbene, which triggers a tandem process involving intermolecular nucleophilic attack and intramolecular SN2 reaction. A series of 5-iodo-1,2,3,4-tetrahydropyridines are obtained in high yield, and the synthetic utility of the products is demonstrated in cross-coupling reactions and the construction of biorelated polycyclic

  碘化钠首次用作亲核试剂来捕获α-亚氨基铑卡宾，这引发了涉及分子间亲核攻击和分子内S N 2反应的串联过程。以高收率获得了一系列的5-碘-1,2,3,4-四氢吡啶，并且在交叉偶联反应和生物相关多环化合物的构建中证明了该产物的合成效用。
• Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols
  作者：Daniels Posevins、Man-Bo Li、Erik Svensson Grape、A. Ken Inge、Youai Qiu、Jan-E. Bäckvall

  DOI：10.1021/acs.orglett.9b04134

  日期：2020.1.17

  A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis-fused [5,5] bicyclic γ-lactones and γ-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels-Alder reaction with N-phenylmaleimide

  开发了钯催化烯醇的氧化级联羰基碳环化反应。在温和的反应条件下，以高收率和高非对映选择性获得了一系列具有1,3-二烯基序的顺式[5,5]双环γ-内酯和γ-内酰胺。所获得的内酯/内酰胺产物是用于与N-苯基马来酰亚胺进行立体选择性Diels-Alder反应的可行底物，从而提供了具有更高分子复杂性的多环化合物。
• Total Synthesis of the Proposed Structure of 8-Deshydroxyajudazol A: A Modified Approach to 2,4-Disubstituted Oxazoles
  作者：Stephen Birkett、Danny Ganame、Bill C. Hawkins、Sébastien Meiries、Tim Quach、Mark A. Rizzacasa

  DOI：10.1021/jo302055w

  日期：2013.1.4

  The total synthesis of the proposed structure for the minor Myxobacterial metabolite 8-deshydroxyajudazol A (3) is described. The isochromanone moiety present in the eastern fragment was constructed by an intramolecular-Diels-Alder (IMDA). Difficulties were encountered with the formation of the 2,4-disubstituted oxazole, so this was synthesized via a modified approach. This involved selective acylation of the diol 7 with acid 8, azide displacement of the secondary alcohol, and subsequent azide reduction in the presence of base which induced an O,N shift to give the hydroxyamide 23. Cyclodehydration then gave the desired oxazole 24 and deprotection followed by mesylation and elimination produced the C15 alkene S. Sonogashira coupling with the eastern fragment vinyl iodide 6 and partial reduction yielded 8-deshydroxyajudazol A (3).