(S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene | 136981-88-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: (S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene
• 英文别名: (Z,S)-1-methyl-3-methoxymethoxy-2-propenyl tributylstannane；(3S,1Z)-3-(tri-n-butylstannyl)-1-(methoxymethoxy)-1-butene；tributyl-[(Z,2R)-4-(methoxymethoxy)but-3-en-2-yl]stannane
• CAS: 136981-88-9
• 化学式: C₁₈H₃₈O₂Sn
• 分子量: 405.209
• InChiKey: FVUIUPLNKMLNIA-HCLDKOLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  21
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene 在 三氟化硼乙醚 、 四丁基氟化铵 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Addition of Enantioenrichedγ-Oxygenated Allylic Stannanes toN-Acyl Iminium Intermediates: A New Synthesis ofsyn-Amino Alcohol Derivatives

  摘要：

  DOI：

  10.1002/(sici)1521-3773(20000303)39:5<953::aid-anie953>3.0.co;2-i
• 作为产物：
  描述：

  (S)-α-(Methoxymethoxy)crotyl tri-n-butylstannane 在 三(五氟苯基)硼烷 碳酸氢钠 作用下， 以 甲苯 为溶剂， 以66%的产率得到(S)-(Z)-1-(Methoxymethoxy)-3-(tri-n-butylstannyl)-1-butene
  参考文献：
  名称：

  The BF3 and B(C6F5)3-catalyzed 1,3-isomerization of allylic stannanes

  摘要：

  A spectroscopic and chemical study of the stereospecific B(C6F5)(3)-catalyzed 1,3-isomerization of (E,S)-1-methoxymethoxy-2-butenyl tributylstannane to (Z,S)-1-methyl-3-methoxymethoxy-2-propenyl tributylstannane is described. A pathway involving an intermediate B(C6F5)(3) adduct is proposed based upon H-1- and Sn-119-NMR data. Analogous spectral evidence was not observed in the seemingly related BF3. OEt2-catalyzed isomerization. However, the similar product ratios obtained in B(C6F5)(3) and BF3. OEt2-promoted additions of the latter stannane to o- and p-methoxybenzaldehyde reveals a close similarity between the two and prompts speculation that the BF3. OEt2-catalyzed 1,3-isomerization proceeds by an analogous pathway. A pathway for the B(C6F5)(3)-promoted addition of allylic stannanes to o-methoxybenzaldehyde is also presented. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00642-8

文献信息

• Marshall, James A.; Welmaker, Gregory S.; Gung, Benjamin W., Journal of the American Chemical Society, 1991, vol. 113, # 2, p. 647 - 656
  作者：Marshall, James A.、Welmaker, Gregory S.、Gung, Benjamin W.

  DOI：——

  日期：——
• Synthesis of anti-Homoallylic Alcohols and Monoprotected 1,2-Diols through InCl3-Promoted Addition of Allylic Stannanes to Aldehydes
  作者：James A. Marshall、Kevin Hinkle

  DOI：10.1021/jo00112a005

  日期：1995.4
• Synthesis of Protected Carbohydrate Derivatives Through Homologation of Threose and Erythrose Derivatives with Chiral .gamma.-Alkoxy Allylic Stannanes
  作者：James A. Marshall、Boris M. Seletsky、George P. Luke

  DOI：10.1021/jo00091a034

  日期：1994.6

  Additions of the gamma-alkoxy allylic stannanes (S)-1 and (R)-1 and the racemate (RS)-1 to the threose and erythrose aldehyde derivatives 6 and 15 in the presence of BF3.OEt(2) or MgBr2.OEt(2) were examined in order to establish stereochemical preferences. It was found that (S)-1 and aldehyde 6 afforded the syn,anti,syn adduct 7 in the BF3-promoted reaction, while (R)-1 and 6 gave the syn,syn,syn adduct 8 under MgBr2 conditions. Likewise, (S)-1 and aldehyde 15 yielded the syn,anti,anti adduct 16 with BF3, whereas (R)-1 and 15 led to the syn,syn,anti adduct 17 with MgBr2. The MgBr2-promoted reactions showed sufficient rate differences between the matched and mismatched stannanes to allow the use of racemic stannane (RS)-1 in just over 2-fold excess, whereupon the matched adducts 8 and 17 were favored by greater than 9:1 over the mismatched adducts. The major adducts 7, 8, 16, and 17 were converted to the hexose derivatives 21, 30/31, 34, and 39 by ozonolysis, selective deprotection, and refunctionalization. Adducts 16 and 17 were dihydroxylated with OsO4-NMO to the deoxyoctose precursors 40/41 and 42/43.
• On the Relative Reactivities of Allyl, Crotyl, α-Oxygenated Crotyl, γ-Oxygenated α-Methylallyl, and Allenyl Tri-<i>n</i>-butylstannane Reagents in Lewis Acid Promoted Additions to Aldehydes
  作者：James A. Marshall、Jill A. Jablonowski、Gregory S. Welmaker

  DOI：10.1021/jo9519975

  日期：1996.1.1
• 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.