(3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-1-pyrroline N-oxide | 154878-81-6

• 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: (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-1-pyrroline N-oxide
• 英文别名: (3S,4S)-3,4-dihydro-3,4-di(t-butyldiphenylsilyloxy)-2H-pyrrole 1-oxide；(3S,4S)-(+)-3,4-bis<(tert-butyldiphenylsilyl)oxy>-3,4-dihydro-2H-pyrrole 1-oxide；tert-butyl-[[(3S,4S)-3-[tert-butyl(diphenyl)silyl]oxy-1-oxido-3,4-dihydro-2H-pyrrol-1-ium-4-yl]oxy]-diphenylsilane
• CAS: 154878-81-6
• 化学式: C₃₆H₄₃NO₃Si₂
• 分子量: 593.913
• InChiKey: LAYPNCPIGUGALP-HEVIKAOCSA-N

物化性质

• 沸点：
  645.3±55.0 °C(predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.47
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-1-pyrroline N-oxide 在 三氟甲磺酸三甲基硅酯 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.25h， 生成 [4S(4α,5β,5aβ,5bα,8aα)]-hexahydro-4,5-di(t-butyldiphenylsilyloxy)-pyrrolo[1,2-b]furo[2,3-d]isoxazol-7(3H)one
  参考文献：
  名称：

  由三甲基甲硅烷基硫酸盐促进的2-三甲基甲硅烷基氧基呋喃加成至手性环氮；[1S（1α，2β，7β，8α，8aα）]-1,2-二（叔丁基二苯基甲硅烷氧基）-吲哚唑烷-7,8-二醇的短合成

  摘要：

  三甲基甲硅烷，三氟甲磺酸促进加入2- trimethylsilyloxyfuran至（3小号，4小号）-3,4-二氢-3,4-二（吨-butyldiphenylsilyloxy）-2H-吡咯-1-氧化物，从（派生- [R ，- [R ） -酒石酸显示出完全的面部选择性，以优异的总收率提供了两种非对映异构的丁烯内酯。主要加合物经历硅胶诱导的闭环反应，得到几乎定量的产率[4 S（4α，5β，5aβ，5bα，8aα）]-六氢-4,5-二（叔丁基二苯基甲硅烷氧基）-吡咯[1， 2- b ]呋喃并[2,3 d ]异恶唑-7-（3H）酮; 用DIBAH还原，然后在Pd（OH）2上进行氢解/ C提供部分保护的1,2,7,8-吲哚并咪唑四醇。

  DOI：

  10.1016/s0040-4020(99)01001-7
• 作为产物：
  描述：

  (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-N-benzylpyrrolidine 在 palladium dihydroxide selenium(IV) oxide 、 氢气 、 双氧水 作用下， 以 甲醇 、 丙酮 为溶剂， 20.0 ℃ 、413.69 kPa 条件下， 反应 74.0h， 生成 (3S,4S)-3,4-Bis<(tert-butyldiphenylsilyl)oxy>-1-pyrroline N-oxide
  参考文献：
  名称：

  Assignment of the Absolute Configuration of Natural Lentiginosine by Synthesis and Enzymic Assays of Optically Pure (+) and (-)-Enantiomers

  摘要：

  The structure and absolute configuration of natural lentiginosine isolated from plant sources was determined to be (1S,2S,8aS)-1,2-dihydroxyindolizidine ((+)-4) on the basis of the synthesis of both enantiomers (+)-4 and (-)-4 and their inhibition of amyloglucosidases. Alkaloid (+)-4 was derived from (L)-(+)-tartaric acid via a highly stereo- and regioselective 1,3-dipolar cycloaddition of (3S,4S)-3 ,4-bis[(tert-butyldiphenylsilyl)oxy]-1-pyrroline N-oxide to methylenecyclopropane, followed by thermal rearrangement of the adduct into (1S,2S,8aS)-1,2-[(tert-butyldiphenylsily)oxy]octahydroindolizin-7-one. The enantiomer (-)-4 was derived in the same way from (D)-(-)-tartaric acid. Both (+)-4 and (-)-4 displayed inhibition specificity for amyloglucosidases, being inactive toward 17 other glycosidases. With amyloglucosidase from Aspergillus niger, synthetic (+)-4 displayed inhibition (K-i = 2 mu M) 5 times stronger than that reported for natural lentiginosine, 35 times that measured for (-)-4, and twice that of castanospermine. Alkaloid (+)-4 is thus the most potent and specific competitive inhibitor of amyloglucosidases among azasugars and their analogues.

  DOI：

  10.1021/jo00126a033

文献信息

• Synthesis of lentiginosine by stereoselective chiral nitrone cycloaddition and thermal rearrangement of strained spiroisoxazolidine
  作者：Franca M. Cordero、Stefano Cicchi、Andrea Goti、Alberto Brandi

  DOI：10.1016/s0040-4039(00)76008-4

  日期：1994.1

  The total synthesis of Lentiginosine (3) is reported. The strategy is based on the 1,3-dipolar cycloaddition of a TBDPS protected 3,4-dihydroxypyrroline N-oxide to methylenecyclopropane followed by the thermal rearrangement of the resulting spirocyclopropaneisoxazolidine to give the functionalised indolizidine skeleton. The compound shows an [α]D value identical, but opposite in sign, with that reported

  报告了Lentiginosine（3）的总合成。该策略基于将TBDPS保护的3,4-二羟基吡咯啉N-氧化物的1,3-偶极环加成至亚甲基环丙烷，然后将所得的螺环丙烷异恶唑烷进行热重排，以得到官能化的吲哚并立定骨架。该化合物的[α] D值与报道的天然异构体相同，但符号相反，但具有相同的绝对构型。
• Kinetic Resolution in 1,3-Dipolar Cycloaddition of Tartaric Acid-Derived Nitrones to 2,3-Dihydro-1-phenyl-1H-phospholes. An Enantioselective Approach to the 2,2'-Coupled Pyrrolidine-Phospholane Ring System
  作者：Alberto Brandi、Stefano Cicchi、Andrea Goti、Marek Koprowski、K. Michal Pietrusiewicz

  DOI：10.1021/jo00085a019

  日期：1994.3

  Enantiomerically pure five-membered ring nitrones derived from L-tartaric acid via C2-symmetric O,O'-protected 3,4-dihydroxy pyrrolidines undergo highly regio- and stereoselective cycloaddition reactions with racemic 2,3-dihydro-1-phenyl-1H-phosphole 1-oxide and 1-sulfide. In all cases formation of only two diastereomeric cycloadducts is observed and their ratio (up to 10:1) is dependent on the size of the protecting groups in the nitrone and on the extent of conversion. The tricyclic cycloadducts feature 2,2'-connection of pyrrolidine and phospholane rings and six contiguous stereogenic centers of which three are created and the one at phosphorus is kinetically resolved during the cycloaddition process. It is established that in the studied kinetic resolutions the stereoselectivity factor 8 = k(S)/k(R) exceeds the value of 10 (up to 14) in the most favorable cases. In a properly tuned reaction both the diastereomeric cycloadducts and the enantiomerically enriched dihydrophosphole derivative can be simultaneously obtained in satisfactory chemical and optical yields.
• Assignment of the Absolute Configuration of Natural Lentiginosine by Synthesis and Enzymic Assays of Optically Pure (+) and (-)-Enantiomers
  作者：Alberto Brandi、Stefano Cicchi、Franca M. Cordero、Roberta Frignoli、Andrea Goti、Sylviane Picasso、Pierre Vogel

  DOI：10.1021/jo00126a033

  日期：1995.10

  The structure and absolute configuration of natural lentiginosine isolated from plant sources was determined to be (1S,2S,8aS)-1,2-dihydroxyindolizidine ((+)-4) on the basis of the synthesis of both enantiomers (+)-4 and (-)-4 and their inhibition of amyloglucosidases. Alkaloid (+)-4 was derived from (L)-(+)-tartaric acid via a highly stereo- and regioselective 1,3-dipolar cycloaddition of (3S,4S)-3 ,4-bis[(tert-butyldiphenylsilyl)oxy]-1-pyrroline N-oxide to methylenecyclopropane, followed by thermal rearrangement of the adduct into (1S,2S,8aS)-1,2-[(tert-butyldiphenylsily)oxy]octahydroindolizin-7-one. The enantiomer (-)-4 was derived in the same way from (D)-(-)-tartaric acid. Both (+)-4 and (-)-4 displayed inhibition specificity for amyloglucosidases, being inactive toward 17 other glycosidases. With amyloglucosidase from Aspergillus niger, synthetic (+)-4 displayed inhibition (K-i = 2 mu M) 5 times stronger than that reported for natural lentiginosine, 35 times that measured for (-)-4, and twice that of castanospermine. Alkaloid (+)-4 is thus the most potent and specific competitive inhibitor of amyloglucosidases among azasugars and their analogues.
• Trimethylsilyltriflate-Promoted Addition of 2-Trimethylsilyloxyfuran to a Chiral Cyclic Nitrone; a Short Synthesis of [1S(1α,2β,7β,8α,8aα)]-1,2-Di(t-butyldiphenylsilyloxy)-indolizidine-7,8-diol
  作者：Marco Lombardo、Claudio Trombini

  DOI：10.1016/s0040-4020(99)01001-7

  日期：2000.1

  The trimethylsilyl triflate promoted addition of 2-trimethylsilyloxyfuran to (3S,4S)-3,4-dihydro-3,4-di(t-butyldiphenylsilyloxy)-2H-pyrrole 1-oxide, derived from (R,R)-tartaric acid, displays complete facial selectivity, affording two diastereomeric butenolides in excellent overall yield. The major adduct undergoes silica-gel induced ring-closure to give in almost quantitative yield [4S(4α,5β,5aβ,5bα

  三甲基甲硅烷，三氟甲磺酸促进加入2- trimethylsilyloxyfuran至（3小号，4小号）-3,4-二氢-3,4-二（吨-butyldiphenylsilyloxy）-2H-吡咯-1-氧化物，从（派生- [R ，- [R ） -酒石酸显示出完全的面部选择性，以优异的总收率提供了两种非对映异构的丁烯内酯。主要加合物经历硅胶诱导的闭环反应，得到几乎定量的产率[4 S（4α，5β，5aβ，5bα，8aα）]-六氢-4,5-二（叔丁基二苯基甲硅烷氧基）-吡咯[1， 2- b ]呋喃并[2,3 d ]异恶唑-7-（3H）酮; 用DIBAH还原，然后在Pd（OH）2上进行氢解/ C提供部分保护的1,2,7,8-吲哚并咪唑四醇。