(2S,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxyheptan-2-ol | 166883-56-3

• 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: (2S,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxyheptan-2-ol
• CAS: 166883-56-3
• 化学式: C₁₄H₃₂O₃Si
• 分子量: 276.492
• InChiKey: KQOOJMJPCJLYTH-YNEHKIRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxyheptan-2-ol 在 四丁基氟化铵 、 4-甲基苯磺酸吡啶 作用下， 生成 (4S,5R,6R)-5-Methoxy-2,2,4-trimethyl-6-propyl-[1,3]dioxane
  参考文献：
  名称：

  Lewis Acid Promoted Additions of .gamma.-Alkoxy- and -(Silyloxy)crotylstannanes to (S)-2-(Benzyloxy)propanal

  摘要：

  Additions of the gamma-oxygenated allylic stannane MOM ethers (R)-1a, (S)-1a, and silyl ethers (R)-1b, (S)-1b to (S)-2-(benzyloxy)propanal (2) in the presence of BF3.OEt(2) and MgBr2 were examined in order to establish matched and mismatched preferences. In the BF3 reactions, stannanes (R)-1a and (R)-1b were matched with 2. The former gave the syn adduct 3 and the cyclopropane 4 as a 93:7 mixture. The OTBS stannanes (R)-1b and (S)-1b gave only the syn adducts 7 and 9, respectively. However, in each case considerable cyclopropane adduct, 8 and 10 respectively, was also formed. When aldehyde 2 was treated with excess racemic stannane, (RS)-1a, adduct 3 derived from (R)-1a was the major product, whereas with (RS)-1b, products 7 and 8 derived from (R)-1b were formed preferentially. Aldehyde 2 showed a preference for MOM ether (S)-1a in the MgBr2-promoted reaction, but each of the enantiomeric OTBS stannanes (R)-1b and (S)-1b afforded a single product, the (Z)-syn,syn alcohol 13 from the former and the (E)-syn,syn. alcohol 9 from the latter. With excess (RS)-1b, aldehyde 2 reacted fastest with (R)-1b, in contrast to the MOM analogue(RS)-1a. The racemic (E) stannanes (E)-1a and (E)-1b were likewise examined. In the BF3 reaction, the major products (5 from the MOM ether (E)-1a and 9 from the silyl ether (E)-1b) were derived from the (R)-enantiomer. With MgBr2, the OMOM stannane (E)-1a gave rise to a mixture of four adducts arising from both the (R) and (S) enantiomers of the stannane. The OTBS stannane (E)-1b, on the other hand, afforded mainly adduct 9 derived from the (R) enantiomer of stannane (E)-1b.

  DOI：

  10.1021/jo00104a046
• 作为产物：
  描述：

  (Z)-1-((tert-Butyldimethylsilyl)oxy)-3-(tri-n-butylstannyl)-1-butene 在 palladium on activated charcoal 氢气 、 magnesium bromide 作用下， 生成 (2S,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxyheptan-2-ol
  参考文献：
  名称：

  Lewis Acid Promoted Additions of .gamma.-Alkoxy- and -(Silyloxy)crotylstannanes to (S)-2-(Benzyloxy)propanal

  摘要：

  Additions of the gamma-oxygenated allylic stannane MOM ethers (R)-1a, (S)-1a, and silyl ethers (R)-1b, (S)-1b to (S)-2-(benzyloxy)propanal (2) in the presence of BF3.OEt(2) and MgBr2 were examined in order to establish matched and mismatched preferences. In the BF3 reactions, stannanes (R)-1a and (R)-1b were matched with 2. The former gave the syn adduct 3 and the cyclopropane 4 as a 93:7 mixture. The OTBS stannanes (R)-1b and (S)-1b gave only the syn adducts 7 and 9, respectively. However, in each case considerable cyclopropane adduct, 8 and 10 respectively, was also formed. When aldehyde 2 was treated with excess racemic stannane, (RS)-1a, adduct 3 derived from (R)-1a was the major product, whereas with (RS)-1b, products 7 and 8 derived from (R)-1b were formed preferentially. Aldehyde 2 showed a preference for MOM ether (S)-1a in the MgBr2-promoted reaction, but each of the enantiomeric OTBS stannanes (R)-1b and (S)-1b afforded a single product, the (Z)-syn,syn alcohol 13 from the former and the (E)-syn,syn. alcohol 9 from the latter. With excess (RS)-1b, aldehyde 2 reacted fastest with (R)-1b, in contrast to the MOM analogue(RS)-1a. The racemic (E) stannanes (E)-1a and (E)-1b were likewise examined. In the BF3 reaction, the major products (5 from the MOM ether (E)-1a and 9 from the silyl ether (E)-1b) were derived from the (R)-enantiomer. With MgBr2, the OMOM stannane (E)-1a gave rise to a mixture of four adducts arising from both the (R) and (S) enantiomers of the stannane. The OTBS stannane (E)-1b, on the other hand, afforded mainly adduct 9 derived from the (R) enantiomer of stannane (E)-1b.

  DOI：

  10.1021/jo00104a046

文献信息

• Lewis Acid Promoted Additions of .gamma.-Alkoxy- and -(Silyloxy)crotylstannanes to (S)-2-(Benzyloxy)propanal
  作者：James A. Marshall、Jill A. Jablonowski、George P. Luke

  DOI：10.1021/jo00104a046

  日期：1994.12

  Additions of the gamma-oxygenated allylic stannane MOM ethers (R)-1a, (S)-1a, and silyl ethers (R)-1b, (S)-1b to (S)-2-(benzyloxy)propanal (2) in the presence of BF3.OEt(2) and MgBr2 were examined in order to establish matched and mismatched preferences. In the BF3 reactions, stannanes (R)-1a and (R)-1b were matched with 2. The former gave the syn adduct 3 and the cyclopropane 4 as a 93:7 mixture. The OTBS stannanes (R)-1b and (S)-1b gave only the syn adducts 7 and 9, respectively. However, in each case considerable cyclopropane adduct, 8 and 10 respectively, was also formed. When aldehyde 2 was treated with excess racemic stannane, (RS)-1a, adduct 3 derived from (R)-1a was the major product, whereas with (RS)-1b, products 7 and 8 derived from (R)-1b were formed preferentially. Aldehyde 2 showed a preference for MOM ether (S)-1a in the MgBr2-promoted reaction, but each of the enantiomeric OTBS stannanes (R)-1b and (S)-1b afforded a single product, the (Z)-syn,syn alcohol 13 from the former and the (E)-syn,syn. alcohol 9 from the latter. With excess (RS)-1b, aldehyde 2 reacted fastest with (R)-1b, in contrast to the MOM analogue(RS)-1a. The racemic (E) stannanes (E)-1a and (E)-1b were likewise examined. In the BF3 reaction, the major products (5 from the MOM ether (E)-1a and 9 from the silyl ether (E)-1b) were derived from the (R)-enantiomer. With MgBr2, the OMOM stannane (E)-1a gave rise to a mixture of four adducts arising from both the (R) and (S) enantiomers of the stannane. The OTBS stannane (E)-1b, on the other hand, afforded mainly adduct 9 derived from the (R) enantiomer of stannane (E)-1b.