(3R,4S,5S)-4-[(tert-butyldimethylsilanyl)oxy]-3,5-dimethyltetrahydropyran-2-one | 444105-66-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3R,4S,5S)-4-[(tert-butyldimethylsilanyl)oxy]-3,5-dimethyltetrahydropyran-2-one
• 英文别名: (3R,4S,5S)-4-(tert-butyldimethylsilanyloxy)-3,5-dimethyltetrahydropyran-2-one；(3R,4S,5S)-4-tert-butyl-dimethyl-silanyloxy-3,5-dimethyl-tetrahydro-pyran-2-one；(3R,4S,5S)-4-[tert-butyl(dimethyl)silyl]oxy-3,5-dimethyloxan-2-one
• CAS: 444105-66-2
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: GPFONLRHFZWMIM-AXFHLTTASA-N

物化性质

• 熔点：
  53-54 °C
• 沸点：
  308.5±35.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.21
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4S,5S)-4-[(tert-butyldimethylsilanyl)oxy]-3,5-dimethyltetrahydropyran-2-one 在 pyridine-SO3 complex 、 三甲基铝 、 四氯化钛 、 三乙胺 作用下， 生成 (3R,4S,5S,6S)-6-allyl-4-tert-butyldimethylsilyloxy-3,5-dimethyltetrahydropyran-2-one
  参考文献：
  名称：

  由甲基丙烯醛方便地合成（2 R，3 S，4 R）-3-（叔丁基二甲基硅烷基氧基）-2,4-二甲基-5-氧戊酸甲氧基甲基酰胺。（+）-discodermolide的C1-C7和C17-C24片段的制备

  摘要：

  描述了两种新的高度立体选择性的途径，以生成（2 R，3 S，4 R）-3-（叔丁基二甲基硅烷基氧基）-2,4-二甲基-5-氧戊酸甲氧基甲基酰胺，这是天然产物合成中的重要中间体。与先前报道的方法相比，这两种方案都明显更短且更便宜。然后将标题化合物转化为有效的微管稳定剂（+）-discodermolide的C1-C7和C17-24片段的直接前体。

  DOI：

  10.1016/s0957-4166(02)00261-6
• 作为产物：
  描述：

  (3R,4S)(E)-6-cyclohexyl-2,4-dimethylhexa-1,5-dien-3-ol 在 2,6-二甲基吡啶 、 manganese(IV) oxide 、 9-borabicyclo[3.3.1]nonane dimer 、 臭氧 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 74.5h， 生成 (3R,4S,5S)-4-[(tert-butyldimethylsilanyl)oxy]-3,5-dimethyltetrahydropyran-2-one
  参考文献：
  名称：

  Scalable, Catalytic Asymmetric Synthesis of Syn, Anti Stereotriad Building Blocks for Polypropionate Antibiotics

  摘要：

  Asymmetric catalysis and chirality transfer by the 2,3-Wittig rearrangement were combined to provide a syn, anti stereotriad-containing olefinic alcohol in five steps from inexpensive starting materials. Development of this compound, a versatile intermediate for polypropionate synthesis, gave known building blocks for discodermolide.

  DOI：

  10.1021/ol0612612

文献信息

• [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。
• Evolution of a Gram-Scale Synthesis of (+)-Discodermolide
  作者：Amos B. Smith、Thomas J. Beauchamp、Matthew J. LaMarche、Michael D. Kaufman、Yuping Qiu、Hirokazu Arimoto、David R. Jones、Kaoru Kobayashi

  DOI：10.1021/ja0015287

  日期：2000.9.1

  stereocontrolled total synthesis of the potent antimitotic agent (+)-discodermolide (1) has been achieved on gram scale. Key elements of the successful strategy include (1) elaboration of three advanced fragments from a common precursor (CP) which embodies the repeating stereochemical triad of the discodermolide backbone, (2) σ-bond installation of the Z trisubstituted olefin, exploiting a modified Negishi cross-coupling

  有效的、高度收敛的、立体控制的有效抗有丝分裂剂 (+)-discodermolide (1) 的全合成已在克级实现。成功策略的关键要素包括 (1) 从共同前体 (CP) 精心制作三个高级片段，该片段体现了 discodermolide 主链的重复立体化学三元组，(2) Z 三取代烯烃的 σ 键安装，利用改进的 Negishi交叉偶联反应，(3) 利用高压合成后期鏻盐，以及 (4) Z 双取代烯烃和末端 (Z)-二烯的 Wittig 安装。
• High 1,5-Anti Stereoinduction in Boron-Mediated Aldol Reactions of Methyl Ketones
  作者：Luiz C. Dias、Rosana Z. Baú、Márcio A. de Sousa、J. Zukerman-Schpector

  DOI：10.1021/ol026968c

  日期：2002.11.1

  [reaction: see text] We report herein a very efficient and synthetically useful 1,4-anti-1,5-anti boron-mediated aldol reaction of a chiral alpha-methyl-beta-alkoxy methyl ketone with achiral aldehydes.

  [反应：见正文]我们在此报告了一种非常有效且合成上有用的1,4-抗-1,5-抗硼介导的手性α-甲基-β-烷氧基甲基酮与非手性醛的羟醛反应。
• [EN] SYNTHESIS OF DISCODERMOLIDE<br/>[FR] SYNTHESE DU DISCODERMOLIDE
  申请人：NOVARTIS AG

  公开号：WO2004009574A1

  公开（公告）日：2004-01-29

  The invention relates to a process for preparing discodermolide, for preparing intermediates for the manufacture of discodermolide and discodermolide analogues and to the intermediates obtained during the process. Wherein the process proceeds via a tetraene of formula (IV).

  该发明涉及一种制备discodermolide的过程，用于制备制造discodermolide和discodermolide类似物的中间体，以及在过程中获得的中间体。其中，该过程通过式（IV）的四烯体进行。
• Studies on the total synthesis of sanglifehrin A: stereoselective synthesis of the C(29)–C(39) fragment
  作者：Luiz C. Dias、Airton G. Salles

  DOI：10.1016/j.tetlet.2006.01.105

  日期：2006.3

  A highly stereoselective synthesis of the C(29)–C(39) fragment of the potent immunosuppressant sanglifehrin A has been accomplished by a sequence involving 16 steps (18% overall yield) from N-propionyloxazolidinone 9. Key steps are a diastereoselective hydroboration, and a diastereoselective epoxidation of an allylic alcohol followed by a 1,5-anti boron-mediated aldol reaction of methyl ketone 4 with

  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。