4(R),5(R)-bis(tert-butyldimethylsilyl)oxyoctadialdehyde | 177854-08-9

• 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: 4(R),5(R)-bis(tert-butyldimethylsilyl)oxyoctadialdehyde
• 英文别名: (4R,5R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]octanedial
• CAS: 177854-08-9
• 化学式: C₂₀H₄₂O₄Si₂
• 分子量: 402.722
• InChiKey: VNCMKUCJEWLIJD-QZTJIDSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  26
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4(R),5(R)-bis(tert-butyldimethylsilyl)oxyoctadialdehyde 在 Rh/Al₂O₃ 吡啶 、 chromium dichloride 、 4-二甲氨基吡啶 、 indium(III) chloride 、 草酰氯 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 三乙基硼氢化锂 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 31.67h， 生成 (2R,5R,2'R,5'R)-5-[(1R,6S)-1,6-Bis-(2-trimethylsilanyl-ethoxymethoxy)-undecyl]-5'-[(E)-(R)-7-iodo-1-(2-trimethylsilanyl-ethoxymethoxy)-hept-6-enyl]-octahydro-[2,2']bifuranyl
  参考文献：
  名称：

  Total Synthesis of the Annonaceous Acetogenins Asiminocin and Asiminecin by a Bidirectional Approach

  摘要：

  A total synthesis of the Annonaceous acetogenins asiminocin and asiminecin is described. The approach is bidirectional starting from the (S,S)-tartrate derived dialdehyde 7 and the (R)-alpha-OSEM stannane 6. Addition of 6 to 7 in the presence of InCl3 afforded the bis-adduct, anti-diol 8. The derived tosylate 9 was converted to the bis-tetrahydrofuran core unit 10 upon treatment with TBAF. Selective silylation of one of the two equivalent terminal diol groupings led to the OTBS ether alcohol 11. Oxidation to aldehyde 12 and then InCl3-promoted addition of the (S)-allylic stannane 14 gave the anti adduct 15. Removal of the OH group by reduction of the tosylate 16 with LiBEt3H yielded the SEM ether 17. Hydrogenation of the three double bonds of 17 followed by cleavage of the terminal silyl ether and oxidation afforded aldehyde 20. Conversion to the vinylic iodide 21 followed by Pd(0)-catalyzed coupling with the (S)-alkynyl butenolide 24 gave the asiminocin derivative 25. Selective hydrogenation of the enyne moiety with diimide and cleavage of the SEM protecting groups completed the synthesis of asiminocin (27). Asiminecin (41) was prepared starting from aldehyde 12 and the OTBS allylic stannane 28. Addition of the latter to the former in the presence of InCl3 afforded the anti adduct 29 which was protected as the SEM ether 30. Hydrogenation followed by OTBS cleavage with TBAF and selective silylation of the primary alcohol with TBSCl and Et3N-DMAP led to the secondary alcohol 33. Tosylation and hydrogenolysis with LiEt3BH removed the C30 OTs group affording the SEM ether 35. The remaining steps were carried out along the lines described for asiminocin via the vinyl iodide 38 which was coupled with acetylenic butenolide 24 to afford enyne 39. Selective reduction with diimide and SEM cleavage completed the synthesis.

  DOI：

  10.1021/jo970424k
• 作为产物：
  描述：

  di-tert-butyl (E)-oct-4-enedioate 在 咪唑 、 AD-mix-β 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 4.75h， 生成 4(R),5(R)-bis(tert-butyldimethylsilyl)oxyoctadialdehyde
  参考文献：
  名称：

  Double Intramolecular S_N‘ O-Cyclization for Stereoselective Synthesis of Bistetrahydrofuran Core of Acetogenins

  摘要：

  A C-2-symmetric bistetrahydrofuran core of acetogenins has been prepared via double intramolecular S-N' O-cyclization reactions. Approaches using readily prepared both E- and Z-olefin substrates are investigated. The cyclization of E-olefins gave a mixture of two diastereomers with low selectivity, while the corresponding Z-olefins predominantly provided a desired trans,trans-bistetrahydrofuran product. The high diastereoselectivity is presumably controlled by a hydrogen-bonding transition state. An efficient enantioselective synthesis of this C-2-symmetric bistetrahydrofuran is also described. Sharpless asymmetric dihydroxylation was used for this approach.

  DOI：

  10.1021/jo981771c

文献信息

• Total Synthesis of the Annonaceous Acetogenin (+)-Asimicin. Development of a New Bidirectional Strategy
  作者：James A. Marshall、Kevin W. Hinkle

  DOI：10.1021/jo970423s

  日期：1997.8.1

  The total synthesis of the Annonaceous acetogenin (+)-asimicin is described. The approach employs the (R)-alpha-OSEM allylic stannane 7 of >95% ee and the dialdehyde 8 obtained from (S,S)-diethyl tartrate. Addition of 7 to 8 in the presence of InCl3 afforded the bis-adduct 9 in 71% yield. Tosylation and treatment with TBAF led to the core bis-tetrahydrofuran intermediate, diol 11, in 78% yield. Mono tosylation (n-BuLi, TsCl, THF-DMSO) and subsequent hydrogenolysis with LiBEt3H gave alcohol 14. The iodide 15 was coupled with the higher-order vinylcyanocuprate to afford olefin 30. This was converted to diol 31 of high ee by the Sharpless protocol. This diol yielded the epoxide 33 via the mono-trisylate 32. Addition of (R)-lithio-2-(OTBS)-3-butyne in the presence of BF3 . OEt2 afforded the alcohol 34. The SEM derivative 35 was treated with TBAF, and the resulting alcohol was converted to the butenolide 38 by a sequence involving treatment with (CF3CO)(2)O, then Pd(PPh3)(4), CO, THF-H2O, and finally AgNO3/silica gel. Cleavage of the SEM protecting group with PPTS in ethanol afforded (+)-asimicin (39).
• 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.
• Total Synthesis of the Annonaceous Acetogenins Asiminocin and Asiminecin by a Bidirectional Approach
  作者：James A. Marshall、Minzhang Chen

  DOI：10.1021/jo970424k

  日期：1997.8.1

  A total synthesis of the Annonaceous acetogenins asiminocin and asiminecin is described. The approach is bidirectional starting from the (S,S)-tartrate derived dialdehyde 7 and the (R)-alpha-OSEM stannane 6. Addition of 6 to 7 in the presence of InCl3 afforded the bis-adduct, anti-diol 8. The derived tosylate 9 was converted to the bis-tetrahydrofuran core unit 10 upon treatment with TBAF. Selective silylation of one of the two equivalent terminal diol groupings led to the OTBS ether alcohol 11. Oxidation to aldehyde 12 and then InCl3-promoted addition of the (S)-allylic stannane 14 gave the anti adduct 15. Removal of the OH group by reduction of the tosylate 16 with LiBEt3H yielded the SEM ether 17. Hydrogenation of the three double bonds of 17 followed by cleavage of the terminal silyl ether and oxidation afforded aldehyde 20. Conversion to the vinylic iodide 21 followed by Pd(0)-catalyzed coupling with the (S)-alkynyl butenolide 24 gave the asiminocin derivative 25. Selective hydrogenation of the enyne moiety with diimide and cleavage of the SEM protecting groups completed the synthesis of asiminocin (27). Asiminecin (41) was prepared starting from aldehyde 12 and the OTBS allylic stannane 28. Addition of the latter to the former in the presence of InCl3 afforded the anti adduct 29 which was protected as the SEM ether 30. Hydrogenation followed by OTBS cleavage with TBAF and selective silylation of the primary alcohol with TBSCl and Et3N-DMAP led to the secondary alcohol 33. Tosylation and hydrogenolysis with LiEt3BH removed the C30 OTs group affording the SEM ether 35. The remaining steps were carried out along the lines described for asiminocin via the vinyl iodide 38 which was coupled with acetylenic butenolide 24 to afford enyne 39. Selective reduction with diimide and SEM cleavage completed the synthesis.
• Double Intramolecular S_N‘ <i>O</i>-Cyclization for Stereoselective Synthesis of Bistetrahydrofuran Core of Acetogenins
  作者：Pan Li、Jiong Yang、Kang Zhao

  DOI：10.1021/jo981771c

  日期：1999.4.1

  A C-2-symmetric bistetrahydrofuran core of acetogenins has been prepared via double intramolecular S-N' O-cyclization reactions. Approaches using readily prepared both E- and Z-olefin substrates are investigated. The cyclization of E-olefins gave a mixture of two diastereomers with low selectivity, while the corresponding Z-olefins predominantly provided a desired trans,trans-bistetrahydrofuran product. The high diastereoselectivity is presumably controlled by a hydrogen-bonding transition state. An efficient enantioselective synthesis of this C-2-symmetric bistetrahydrofuran is also described. Sharpless asymmetric dihydroxylation was used for this approach.