(R)-1-Methyl-4-(1,1,1-trimethylacetoxy)-2-butynyl methanesulfonate | 171011-73-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (R)-1-Methyl-4-(1,1,1-trimethylacetoxy)-2-butynyl methanesulfonate
• 英文别名: [(4R)-4-methylsulfonyloxypent-2-ynyl] 2,2-dimethylpropanoate
• CAS: 171011-73-7
• 化学式: C₁₁H₁₈O₅S
• 分子量: 262.327
• InChiKey: BINMZYBWHTZFCJ-SECBINFHSA-N

物化性质

• 沸点：
  386.8±27.0 °C(Predicted)
• 密度：
  1.167±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-1-Methyl-4-(1,1,1-trimethylacetoxy)-2-butynyl methanesulfonate 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 palladium diacetate 、 lithium aluminium tetrahydride 、 L-(+)-酒石酸二异丙酯 、 diethylzinc 、 三苯基膦 、 红铝 作用下， 以 四氢呋喃 、 癸烷 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 61.0h， 生成 (3R,4S,5R)-4,6-dimethylheptane-1,3,5-triol
  参考文献：
  名称：

  向bafilomycin A（1）的总合成迈进：通过向醛类中添加非外消旋烯基锌试剂来立体选择性合成C15-C25亚基。

  摘要：

  [反应：见正文]巴非霉素A（1）（1）的C15-C25亚基（2）的高度立体选择性合成是通过在醛中添加手性非外消旋烯基锌试剂的方法完成的。

  DOI：

  10.1021/ol006344b
• 作为产物：
  描述：

  (S)-4-(tert-butyl-dimethyl-silanyloxy)-pent-2-yn-1-ol 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (R)-1-Methyl-4-(1,1,1-trimethylacetoxy)-2-butynyl methanesulfonate
  参考文献：
  名称：

  Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506

  摘要：

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.

  DOI：

  10.1021/jo00127a031

文献信息

• Synthesis of the C(7)–C(22) Sector of (+)-Acutiphycin via O-Directed Double Free Radical Alkyne Hydrostannation with Ph₃SnH/Et₃B, Double I–Sn Exchange, and Double Stille Coupling
  作者：Karl J. Hale、Maciej Maczka、Amarjit Kaur、Soraya Manaviazar、Mehrnoosh Ostovar、Milosz Grabski

  DOI：10.1021/ol500050p

  日期：2014.2.21

  Herein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane

  在此，在结构上复杂的二烷基二炔11上报道了新的双O定向的自由基氢氢化反应。通过使用构象抑制性乙缩醛来防止乙烯基中间物损害立体中心损害的1,5-H原子抽象反应，使用Ph 3 SnH / Et 3 B / O同时构建了具有高立体控制性的10个乙烯基锡烷2。然后，通过O-甲硅烷基化和两次I-Sn交换，将Distannane 10精制为双乙烯基碘化物9。9的双Stille偶联，O-去甲硅烷基化和随后的氧化提供8。
• Synthesis of a C20−C26 Segment of Superstolide A by Addition of a Chiral Allenylzinc Reagent to (<i>R</i>)-<i>N</i>-Boc Alaninal
  作者：James A. Marshall、James J. Mulhearn

  DOI：10.1021/ol050289v

  日期：2005.4.14

  Additions of chiral allenylzinc and indium reagents to N-Boc alaninal were examined as a possible route to a C20-C26 segment of superstolide A. Allenylzinc reagents, prepared in situ by palladiozincation of (R)- and (S)-5-pivalyloxy-3-butyn-2-ol mesylate, showed excellent reagent control to afford the anti,syn and anti,anti diastereomers as the nearly exclusive adducts.
• Synthesis of a C22-34 Subunit of the Immunosuppressant FK-506
  作者：James A. Marshall、Shiping Xie

  DOI：10.1021/jo00127a031

  日期：1995.11

  A new route to the C22-34 subunit of FK-506 was developed. A highly diastereoselective Diels-Alder reaction of 1,3-butadiene with the bis-acrylate of (R,R)-hydrobenzoin and subsequent saponification provided the cyclohexenecarboxylic acid 6.4 of 95% ee. Elaboration to the enal 9.2 was effected by known transformations. Enal 9.2 underwent diastereoselective and enantiospecific S(E)2' addition of allenyl stannane (S)-3.9 affording the homopropargylic alcohol 9.3 as an 85:15 syn/anti mixture. The PMB ether 9.5 was converted to the known benzylidene derivative 10.4 by sequential treatment with Red-Al, epoxidation, a second reduction with Red-Al, and oxidative benzylidene formation with DDQ.
• Progress toward the Total Synthesis of Bafilomycin A₁:  Stereoselective Synthesis of the C15−C25 Subunit by Additions of Nonracemic Allenylzinc Reagents to Aldehydes
  作者：James A. Marshall、Nicholas D. Adams

  DOI：10.1021/ol006344b

  日期：2000.9.1

  [reaction: see text] A highly stereoselective synthesis of the C15-C25 subunit (2) of bafilomycin A(1) (1) has been accomplished by a route utilizing additions of chiral nonracemic allenylzinc reagents to aldehydes.

  [反应：见正文]巴非霉素A（1）（1）的C15-C25亚基（2）的高度立体选择性合成是通过在醛中添加手性非外消旋烯基锌试剂的方法完成的。