[[3-(2R,3R)-4R]-3-(3-(tert-butyldimethylsilyloxy)-2,4-dimethyl-1-oxopent-4-enyl)-4-(phenylmethyl)]-2-oxazolidinone | 565228-87-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: [[3-(2R,3R)-4R]-3-(3-(tert-butyldimethylsilyloxy)-2,4-dimethyl-1-oxopent-4-enyl)-4-(phenylmethyl)]-2-oxazolidinone
• 英文别名: (4R)-4-benzyl-3-[(2R,3R)-3-(tert-butyldimethylsilanyloxy)-2,4-dimethylpent-4-enoyl]oxazolidin-2-one；(4R)-4-benzyl-3-[(2R,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2,4-dimethylpent-4-enoyl]-1,3-oxazolidin-2-one
• CAS: 565228-87-7
• 化学式: C₂₃H₃₅NO₄Si
• 分子量: 417.621
• InChiKey: TXZAFRJUIHDZQY-RLLQIKCJSA-N

物化性质

• 沸点：
  505.0±43.0 °C(Predicted)
• 密度：
  1.053±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.18
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [[3-(2R,3R)-4R]-3-(3-(tert-butyldimethylsilyloxy)-2,4-dimethyl-1-oxopent-4-enyl)-4-(phenylmethyl)]-2-oxazolidinone 在 咪唑 、 4-二甲氨基吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 、 二甲基氯化铝 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 生成 (2R,3S,4S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2,4-dimethylpentanal
  参考文献：
  名称：

  桑格菲林A的总合成研究：C（29）–C（39）片段的立体选择性合成

  摘要：

  在C（29）-C（39）的有效的免疫抑制剂萨菲菌素A的片段的高度立体选择性合成已经由从包括16步（18％总收率）的序列来完成Ñ -propionyloxazolidinone 9。关键步骤是非对映选择性的硼氢化反应，以及烯丙醇的非对映选择性环氧化，然后是甲基酮4与手性醛5的1,5-抗硼介导的羟醛缩合反应。

  DOI：

  10.1016/j.tetlet.2006.01.105
• 作为产物：
  描述：

  (R)-(-)-4-苄基-3-丙酰基-2-恶唑烷酮 在 2,6-二甲基吡啶 、 三氟甲磺酸二丁硼 作用下， 以 二氯甲烷 为溶剂， 反应 10.5h， 生成 [[3-(2R,3R)-4R]-3-(3-(tert-butyldimethylsilyloxy)-2,4-dimethyl-1-oxopent-4-enyl)-4-(phenylmethyl)]-2-oxazolidinone
  参考文献：
  名称：

  螺旋藻A和B的C22-23模型羟醛偶联的立体选择性

  摘要：

  制备了一个模型系统，以研究关键的C22-23醛醇偶合体对合成螺旋藻A和B的非对映选择性。模型3的烯醇锂与不同保护的醛4（丙酮化物）和5（甲硅烷基）结合，在两种情况下，分别使用3：1和3.5：1 dr都支持非天然（S）异构体。由醛保护基诱导的对醛醇的立体选择性没有任何显着影响，这与以前的文献报道形成了对比。

  DOI：

  10.1016/j.tet.2012.10.008

文献信息

• A synthetic approach to the phorboxazoles – Synthesis of the C20–C32 central core
  作者：James W. Leahy、Stephen J. Boyer

  DOI：10.1016/j.tetlet.2017.07.009

  日期：2017.8

  An enantiospecific synthesis of the C20–C32 central core of the phorboxazole scaffold, including the non-macrocyclic oxazole is detailed in 17 steps (longest linear sequence) from methacrolein in 7.8% overall yield. All of the stereocenters are communicated from a single Evans aldol reaction, and the final compound is suitably functionalized for further elaboration to the natural products.

  从甲基丙烯醛以17个步骤（最长的线性序列）详细描述了佛波唑支架（包括非大环恶唑）的C20–C32中央核的对映体特异性合成，总产率为7.8％。所有的立构中心都是通过一个单一的Evans醛醇缩合反应进行的，最终化合物经过适当官能化处理，可以进一步精制天然产物。
• [EN] ANALOGS OF DISCODERMOLIDE AND DICTYOSTATIN-1, INTERMEDIATES THEREFOR AND METHODS OF SYNTHESIS THEREOF<br/>[FR] ANALOGUES DE DISCODERMOLIDE ET DE DICTYOSTATINE-1, INTERMEDIAIRES CORRESPONDANTS, ET PROCEDES DE SYNTHESE CORRESPONDANTS
  申请人：UNIV PITTSBURGH

  公开号：WO2004022552A1

  公开（公告）日：2004-03-18

  A compound of the following structure: wherein R1 is H, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a halogen atom; R2 is H, an alkyl group, an aryl group, a benzyl group, a trityl group, -SiRaRbRc, CH2ORd, or CORe; Ra, Rb and Rc are independently an alkyl group or an aryl group; Rd is an alkyl group, an aryl group, an alkoxylalkyl group, -RiSiRaRbRc or a benzyl group, wherein Ri is an alkylene group; Re is an alkyl group, an allyl group, a benzyl group, an aryl group, an alkoxy group, or -NRgRh, wherein Rg and Rh are independently H, an alkyl group or an aryl group; R3 is (CH2)n where n is and integer in the range of 0 to 5, -CH2CH(CH3)-, -CH=CH-, -CH=C(CH3)-, or -C=-C-; R4 is (CH2)p where p is an integer in the range of 4 to 12, -(CHRkl)yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5C(Rsl )=C(Rs2)C(Rs3)=C(Rs4)-, -(CHRk1 )yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5CH(Rs I)CH(Rs2)C(Rs3)=C(Rs4)-, -(CHRk1)yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRks)y5C(Rsl)=C(Rs2)CH(Rs3)CH(Rs4)-, -(CHRkI )yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5CH(Rsl)CH(Rs2)CH(Rs3)CH(R s4)-, wherein y1 and y2 are 1 and y3, y4 and y5 are independently 0 or 1, Rk1, Rk2, Rk3, Rk4 and Rk5 are independently H, CH3, or OR2a, and Rs1, Rs2, Rs3, and Rs4 are independently H or CH3, wherein R2a is H, an alkyl group, an aryl group, a benzyl group, a trityl group, -SiRaRbRc, CH2ORd, or CORe; and R5 is H or OR2b, wherein R2b is H, an alkyl group, an aryl group, an aryl group, a benzyl group, a trityl group, -SiRaRbRc, CH2ORd, or CORe; provided that the compound is not dictyostatin 1.

  以下是该结构的化合物：其中R1为H、烷基基团、芳基、烯基基团、炔基基团或卤素原子；R2为H、烷基基团、芳基、苄基、三苄基、-SiRaRbRc、CH2ORd或CORe；Ra、Rb和Rc独立地为烷基基团或芳基；Rd为烷基基团、芳基、烷氧基烷基团、-RiSiRaRbRc或苄基，其中Ri为烷基烷基团；Re为烷基基团、烯丙基基团、苄基、芳基、烷氧基或-NRgRh，其中Rg和Rh独立地为H、烷基基团或芳基；R3为(CH2)n，其中n为0到5范围内的整数，-CH2CH(CH3)-、-CH=CH-、-CH=C(CH3)-或-C=-C-；R4为(CH2)p，其中p为4到12范围内的整数，-(CHRkl)yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5C(Rsl )=C(Rs2)C(Rs3)=C(Rs4)-、-(CHRk1 )yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5CH(Rs I)CH(Rs2)C(Rs3)=C(Rs4)-、-(CHRk1)yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRks)y5C(Rsl)=C(Rs2)CH(Rs3)CH(Rs4)-、-(CHRkI )yl (CHRk2)y2(CHRk3)y3(CHRk4)y4(CHRk5)y5CH(Rsl)CH(Rs2)CH(Rs3)CH(R s4)-，其中y1和y2为1，y3、y4和y5独立地为0或1，Rk1、Rk2、Rk3、Rk4和Rk5独立地为H、CH3或OR2a，Rs1、Rs2、Rs3和Rs4独立地为H或CH3，其中R2a为H、烷基基团、芳基、苄基、三苄基、-SiRaRbRc、CH2ORd或CORe；R5为H或OR2b，其中R2b为H、烷基基团、芳基、芳基、苄基、三苄基、-SiRaRbRc、CH2ORd或CORe；前提是该化合物不是dictyostatin 1。
• Total Synthesis of Aflastatin A
  作者：David A. Evans、Jason J. Beiger、Jason D. Burch、Peter H. Fuller、Frank Glorius、Egmont Kattnig、David A. Thaisrivongs、William C. Trenkle、Joseph M. Young、Jing Zhang

  DOI：10.1021/jacs.2c08244

  日期：2022.11.2

  reaction. Careful comparison of the spectroscopic data for the synthetic C3–C48 degradation fragment to that reported by the isolation group revealed a structural misassignment in the lactol region of the naturally derived degradation product. Ultimately, the data reported for the naturally derived aflastatin A C3–C48 degradation lactol (6a, R = H) were attributed to its derivative lactol trideuteriomethyl

  已经完成了黄曲霉毒素A及其C3-C48降解片段（6a，R=H）的全合成。该合成具有几个复杂的非对映选择性片段偶联，包括 Felkin 选择性三苯甲基催化的 Mukaiyama 醛醇反应、螯合物控制的醛醇反应，涉及与镁的软烯醇化，以及抗 Felkin 选择性硼介导的氧化醛醇反应。将合成 C3-C48 降解片段的光谱数据与分离组报告的光谱数据进行仔细比较，揭示了天然衍生降解产物的乳醇区域的结构错误分配。最终，天然来源的黄曲霉毒素 A C3–C48 降解内酯的数据报告 ( 6a, R = H) 归因于它的衍生物 lactol trideuteriomethyl ether ( 6c , R = CD 3 )。此外，确认了六个立体异构中心（C8、C9 和 C28–C31）的修订绝对配置。
• Simplified Discodermolide Analogues:  Synthesis and Biological Evaluation of 4-<i>e</i><i>pi</i>-7-Dehydroxy-14,16-didemethyl-(+)-discodermolides as Microtubule-Stabilizing Agents
  作者：Nakyen Choy、Youseung Shin、Phu Qui Nguyen、Dennis P. Curran、Raghavan Balachandran、Charitha Madiraju、Billy W. Day

  DOI：10.1021/jm0204136

  日期：2003.7.1

  Several novel analogues of (+)-discodermolide were synthesized via a convergent strategy that used Wittig reactions to append left and right side chains to a central scaffold and then tested for biological activity. Three of the analogues in the 4-epi-7-dehydroxy-14,16-didemethyl series, 6a-c, had interesting actions. The C3-methoxymethyl ether analogue 6b was more active in antiproliferative cell-based assays as well as in hypernucleation and paclitaxel site competition assays with isolated tubulin than the other analogues, including 6a, which contained a free hydroxyl group at the C3 position. The biological results validated the initial hypothesis that the C7 hydroxy group and the C14 and C16 methyl groups of (+)-discodermolide could be deleted without undermining activity. Although less potent than (+)-discodermolide and paclitaxel, compounds 6b and 6c both showed properties unique to (+)-discodermolide. These properties, particularly the capacity to cause hypernucleation of isolated tubulin at lower temperature than paclitaxel, as well as stabilizing preformed microtubules to cold disassembly, are considered mechanistically superior to those of paclitaxel. Other variations in the right and left sides of the discodermolide scaffold revealed additional structure/activity information.
• Stereoselectivity of model C22–23 aldol coupling for spirangiens A &amp; B
  作者：Claire Gregg、Michael V. Perkins

  DOI：10.1016/j.tet.2012.10.008

  日期：2013.1

  the key C22–23 aldol coupling for the synthesis of spirangiens A & B. The lithium enolate of model ketone 3 was coupled with the differently protected aldehydes 4 (acetonide) and 5 (silyl) giving 3:1 and 3.5:1 dr, respectively, in favour of the unnatural (S) isomer in both cases. The lack of any significant effect on the aldol stereoselectivity induced by the aldehyde protecting groups contrasts with

  制备了一个模型系统，以研究关键的C22-23醛醇偶合体对合成螺旋藻A和B的非对映选择性。模型3的烯醇锂与不同保护的醛4（丙酮化物）和5（甲硅烷基）结合，在两种情况下，分别使用3：1和3.5：1 dr都支持非天然（S）异构体。由醛保护基诱导的对醛醇的立体选择性没有任何显着影响，这与以前的文献报道形成了对比。