Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate | 121542-15-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate
• 英文别名: Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsilyloxy)-(2E,6E)-octadienedioate；Diethyl (4S,5S)-4,5-bis((tert-butyldimethylsilyl)oxy)-2,6-octadienedioate；diethyl (2E,4S,5S,6E)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]octa-2,6-dienedioate
• CAS: 121542-15-2
• 化学式: C₂₄H₄₆O₆Si₂
• 分子量: 486.797
• InChiKey: GDMVSENXIZFNJM-ZBXVFRPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.01
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4 A molecular sieve 、 二异丁基氢化铝 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 10.0h， 生成 (1R,4S)-4-[(1S,2S)-1,2-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[(1S,4R)-4-hydroxycyclopent-2-en-1-yl]ethyl]cyclopent-2-en-1-ol
  参考文献：
  名称：

  A New Synthetic Route to Nucleosides:  Dissymmetric Construction of a Cyclopentene System by Double [3,3]-Sigmatropic Rearrangement and Double Ring-Closing Metathesis

  摘要：

  [GRAPHICS]The dissymmetric synthesis of a carbocyclic nucleoside was achieved by a novel double [3,3]-sigmatropic rearrangement/double ring-closing metathesis strategy with a high stereoselectivity.

  DOI：

  10.1021/ol040006j
• 作为产物：
  描述：

  diethyl (-)-(4S,5S)-4,5-O-isopropylidene-4,5-dihydroxy-2,6-octadienedioate 在 盐酸 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 Diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate
  参考文献：
  名称：

  Conformational diagnosis of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate based on the stereochemical outcomes of representative reactions as compared with those of its 4,5-O-isopropylidene derivatives and on a dichroic exciton chirality method

  摘要：

  In order to gain more insight into the conformation of diethyl (4S,5S)-4,5-bis(tert-butyldimethylsiloxy)-2E,6E-octadienedioate (1) experimentally, some appropriate reactions of 1 and its derivative (S,S)-3, which bears isopropylidene protecting groups, have been executed. The stereochemical outcomes of such reactions as the Diels-Alder reaction, osmium tetraoxide-catalyzed hydroxylation, conjugate addition with amines, and cyclopropanation with phosphonium ylides point to a rigid conformation (1A) in which the vicinal TBDMSO groups, the most bulky substituents, are arranged in an anti relationship, and, therefore, the enoate groups are forced to be gauche each other. A dichroic exciton chirality study has also provided clear-cut evidence for this rigid conformation.

  DOI：

  10.1021/jo00075a024

文献信息

• Rotamer distribution control and double Michael addition for cyclopentane annulation with superb selectivity
  作者：Seiki Saito、Yohji Hirohara、Osamu Narahara、Toshio Moriwake

  DOI：10.1021/ja00194a078

  日期：1989.6
• An Efficient Bidirectional Approach to the <i>C</i>₂-Symmetric Stereoisomers of the Bistetrahydrofuran Core of the Acetogenins
  作者：James A. Marshall、Kevin W. Hinkle

  DOI：10.1021/jo9603789

  日期：1996.1.1

  A bidirectional route to nonracemic C-2-symmetric bistetrahydrofuran units related to acetogenin natural products was developed starting from the (S,S)-tartrate-derived dialdehyde 3.3. Bis-homologation with the (R)-alpha-OMOM crotylstannane (R)-4.1 in the presence of InCl3 afforded the anti adduct, diol 4.3. The derived tosylate 4.4, upon treatment with TBAF in THF, underwent sequential TBS cleavage and cyclization to the (R,R,R,R,R,R)-bis-OMOM bistetrahydrofuran 4.7. The epimeric (S,R,R,R,R,S)-bis-OMOM bistetrahydrofuran 4.10 was prepared along similar lines, except that the (R)-alpha-OMOM crotylstannane (R)-4.1 was first converted to the (R)-gamma-isomer (R)-4.2 with BF3 . OEt(2). Subsequent addition of dialdehyde 3.3 led to the diol adduct 4.5, which after tosylation and treatment with TBAF, yielded the bistetrahydrofuran 4.10. By repeating the aforementioned sequences, but starting with the (S)-alpha-OMOM-crotylstannane (S)-4.1, the (S,S-R,R,S,S)- and the (R,S,R,R,S,R)-bistetrahydrofurans 5.5 and 5.8 were prepared. A variation on the foregoing sequence in which the OTBS grouping of the adduct was converted to a mesylate and the OH group was used to effect intramolecular displacement was also examined. Accordingly, adduct ent-5.3 from BF3-promoted addition of stannane (R)-4.2 and ent-3.3, the enantiomer of aldehyde 3.3, was acetylated. Cleavage of the TBS ether followed by mesylate formation and then concommitant acetate hydrolysis and cyclization with methanolic Triton B yielded the bis-OMOM bistetrahydrofuran 5.5. An analogous sequence was used to convert adduct 4.3 to ent-4.10. In this case, acetate saponification was effected with methanolic K2CO3, and the resulting diol, 7.4, was cyclized with NaH in THF.
• High differentiation of the diastereo .pi.(C:C)-faces of acyclic bis-allylic systems in osmium tetroxide-catalyzed dihydroxylation
  作者：Seiki Saito、Yasuhisa Morikawa、Toshio Moriwake

  DOI：10.1021/jo00307a002

  日期：1990.9
• Remote Conformational Bias Effects on Diastereofacial Selectivity in SE2' Additions of .gamma.-Oxygenated Allylic Stannanes to Chiral Enals
  作者：James A. Marshall、Serge Beaudoin

  DOI：10.1021/jo00104a047

  日期：1994.12

  The enal 10 derived from (R,R)-diethyl tartrate shows matched/mismatched characteristics in BF3-promoted additions of the chiral gamma-oxygenated allylic stannanes S1, S2, R1, and R2. Both S2 and S1 afford a single syn adduct 11 and 14 with enal 10, whereas R2 and R1 give mixtures of syn and anti products 12/13 and 15/16. Racemic stannane RS2 affords a 82:18 mixture of syn adducts 11 and 12; RS1 gives the two syn adducts 14 and 15 as a 77:23 mixture. The observed facial bias in these additions is attributed to conformational effects engendered by the vicinal syn OTBS substituents which cause enal 10 to adopt a chair-like conformation. The matched additions proceed by attack on the ''outside'' face of the carbonyl grouping in the s-cis orientation of this chair-like arrangement.
• Facile synthesis of a key intermediate for the synthesis of prostanes and isoprostanes
  作者：Subhash P Chavan、Y.Tripura Subbarao、A.G Chittiboyina、R Sivappa、C.G Suresh

  DOI：10.1016/s0957-4166(01)00213-0

  日期：2001.5