1-(tert-butyldiphenylsiloxy)-3-methyl-2-butanone | 136022-54-3

• 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: 1-(tert-butyldiphenylsiloxy)-3-methyl-2-butanone
• 英文别名: 1-(t-butyldiphenylsiloxy)-3-methyl-2-butanone；2-Butanone, 1-[[(1,1-dimethylethyl)diphenylsilyl]oxy]-3-methyl-；1-[tert-butyl(diphenyl)silyl]oxy-3-methylbutan-2-one
• CAS: 136022-54-3
• 化学式: C₂₁H₂₈O₂Si
• 分子量: 340.538
• InChiKey: NLGPUPVRWVURPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(tert-butyldiphenylsiloxy)-3-methyl-2-butanone 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 四丁基氟化铵 、 sodium hydride 、 (-)-diethyl tartrate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 60.5h， 生成 (S)-(+)-2-(hydroxymethyl)-2-isopropylcyclobutanone
  参考文献：
  名称：

  A concise and enantioselective approach to cyclobutanones by tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols. An enantiocontrolled synthesis of (+)- and (-)-.alpha.-cuparenones

  摘要：

  A tandem Katsuki-Sharpless asymmetric epoxidation and enantiospecific ring expansion of 2-alkyl(or 2-aryl)-2-cyclopropylideneethanols (1a-i) afforded chiral 1-alkyl(or 1-aryl)-1-(hydroxymethyl)cyclobutanones (3a-i) in high yields and high enantiomeric excess. These compounds are potentially valuable synthons for the enantioselective creation of the quaternary carbons. Hence, this enabled us to accomplish a concise and enantioselective total synthesis of both (+)- and (-)-alpha-cuparenones (11).

  DOI：

  10.1021/jo00032a021
• 作为产物：
  描述：

  (tert-butyldiphenylsilanyloxy)acetaldehyde 在 重铬酸吡啶 、 4 A molecular sieve 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 1-(tert-butyldiphenylsiloxy)-3-methyl-2-butanone
  参考文献：
  名称：

  A concise and enantioselective approach to cyclobutanones by tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols. An enantiocontrolled synthesis of (+)- and (-)-.alpha.-cuparenones

  摘要：

  A tandem Katsuki-Sharpless asymmetric epoxidation and enantiospecific ring expansion of 2-alkyl(or 2-aryl)-2-cyclopropylideneethanols (1a-i) afforded chiral 1-alkyl(or 1-aryl)-1-(hydroxymethyl)cyclobutanones (3a-i) in high yields and high enantiomeric excess. These compounds are potentially valuable synthons for the enantioselective creation of the quaternary carbons. Hence, this enabled us to accomplish a concise and enantioselective total synthesis of both (+)- and (-)-alpha-cuparenones (11).

  DOI：

  10.1021/jo00032a021

文献信息

• Lewis acid-promoted selective rearrangement of trisubstituted epoxides to aldehydes or ketones
  作者：Keiji Maruoka、Noriaki Murase、Ronan Bureau、Takashi Ooi、Hisashi Yamamoto

  DOI：10.1016/s0040-4020(01)90389-8

  日期：1994.3

  Rearrangement of trisubstituted epoxides has been effected under the influence of various Lewis acids. Among these, methylaluminum bis(4-bromo-2,6-di-tert-butylphenoxide) (MABR) can be selectively rearranged from trisubstituted epoxides to aldehydes, while antimony pentafluoride is employable for selective rearrangement to ketones under mild conditions.
• Maruoka Keiji, Murase Noriaki, Bureau Ronan, Ooi Takashi, Yamamoto Hisash+, Tetrahedron, 50 (1994) N 12, S 3663-3672
  作者：Maruoka Keiji, Murase Noriaki, Bureau Ronan, Ooi Takashi, Yamamoto Hisash+

  DOI：——

  日期：——
• A concise and enantioselective approach to cyclobutanones by tandem asymmetric epoxidation and enantiospecific ring expansion of cyclopropylidene alcohols. An enantiocontrolled synthesis of (+)- and (-)-.alpha.-cuparenones
  作者：Hideo Nemoto、Hiroki Ishibashi、Masatoshi Nagamochi、Keiichiro Fukumoto

  DOI：10.1021/jo00032a021

  日期：1992.3

  A tandem Katsuki-Sharpless asymmetric epoxidation and enantiospecific ring expansion of 2-alkyl(or 2-aryl)-2-cyclopropylideneethanols (1a-i) afforded chiral 1-alkyl(or 1-aryl)-1-(hydroxymethyl)cyclobutanones (3a-i) in high yields and high enantiomeric excess. These compounds are potentially valuable synthons for the enantioselective creation of the quaternary carbons. Hence, this enabled us to accomplish a concise and enantioselective total synthesis of both (+)- and (-)-alpha-cuparenones (11).