(R)-(-)-N-(2-methylheptan-3-ylidene)-2-methylpropane-2-sulfinamide | 220263-60-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 亚磺酸及其衍生物
• 英文名称: (R)-(-)-N-(2-methylheptan-3-ylidene)-2-methylpropane-2-sulfinamide
• 英文别名: (NE,R)-2-methyl-N-(2-methylheptan-3-ylidene)propane-2-sulfinamide
• CAS: 220263-60-5
• 化学式: C₁₂H₂₅NOS
• 分子量: 231.403
• InChiKey: XKXDMKSFUFSZAO-HFBDAHEESA-N

物化性质

• 沸点：
  324.448±25.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  0.965±0.14 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-(-)-N-(2-methylheptan-3-ylidene)-2-methylpropane-2-sulfinamide 在 ruthenium trichloride sodium periodate 、 正丁基锂 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 生成 (R)-2-Isopropyl-2-(2-methyl-propane-2-sulfonylamino)-hexanoic acid
  参考文献：
  名称：

  叔丁烷亚磺酰基酮亚胺不对称合成预保护的α，α-二取代氨基酸

  摘要：

  描述了一种不对称合成预保护的α，α-二取代氨基酸的方法。5- Methylfuryllithium加入到亚硫酮亚胺1中阿尔梅的存在3，得到亚磺酰胺2在75-97％的产率和非对映选择性与范围从75:25至99：1。用的RuCl随后氧化3 /的NaIO 4，得到叔-butanesulfonyl（总线）保护的α，α-二取代的氨基酸3在62-69％的产率。总线保护的氨基酸容易形成酰胺键，此后可以用TfOH / CH 2 Cl 2除去总线基团，得到游离胺。

  DOI：

  10.1016/s0040-4039(00)02300-5
• 作为产物：
  描述：

  2-甲基-3-庚酮 、 (R)-(+)-叔丁基亚磺酰胺 在 titanium(IV) tetraethanolate 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以77%的产率得到(R)-(-)-N-(2-methylheptan-3-ylidene)-2-methylpropane-2-sulfinamide
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones

  摘要：

  Experimental details for the first general methods for the one-step preparation of N-tert-butanesulfinyl imines (tert-butanesulfinimines) (2) from aldehydes and ketones is described. To effect the condensations of tert-butanesulfinamide (1) with aldehydes, the Lewis acidic dehydrating agents MgSO4, CuSO4, or Ti(OEt)(4) are employed. Aldehyde condensations mediated by MgSO4 proceed in high yields (84-96%) when an excess of aldehyde is used. In contrast, only a slight excess of aldehyde (1.1 equiv) relative to tert-butanesulfinamide provides sulfinimines in high yields when the more Lewis acidic dehydrating agent CuSO4 is used. The CuSO4-mediated procedure is effective for a wide range of aldehydes, including sterically demanding aldehydes, such as isobutyraldehyde (90%), and electron-rich aldehydes, such as p-anisaldehyde (81%). The still more Lewis acidic Ti(OEt)(4) and Ti(O-i-Pr)(4) also afford N-tert-butanesulfinyl aldimines from especially unreactive aldehydes, such as pivaldehyde (82%). In addition, Ti(OEt)(4) is effective for the condensation of I with ketones to afford a wide range of N-tert-butanesulfinyl ketimines in good yields (77-91%). For sulfinyl ketimines derived from methyl or n-alkyl phenyl ketones and methyl or n-alkyl isopropyl ketones, only the E isomer is detected by H-1 and C-13 NMR in CDCl3. For those cases where the difference in steric demand about the imine is very small, such as for 2-hexanone, high E/Z ratios are still observed (5:1).

  DOI：

  10.1021/jo982059i

文献信息

• Synthesis of Enantiomerically Pure <i>N</i>-<i>tert</i>-Butanesulfinyl Imines (<i>tert</i>-Butanesulfinimines) by the Direct Condensation of <i>tert</i>-Butanesulfinamide with Aldehydes and Ketones
  作者：Guangcheng Liu、Derek A. Cogan、Timothy D. Owens、Tony P. Tang、Jonathan A. Ellman

  DOI：10.1021/jo982059i

  日期：1999.2.1

  Experimental details for the first general methods for the one-step preparation of N-tert-butanesulfinyl imines (tert-butanesulfinimines) (2) from aldehydes and ketones is described. To effect the condensations of tert-butanesulfinamide (1) with aldehydes, the Lewis acidic dehydrating agents MgSO4, CuSO4, or Ti(OEt)(4) are employed. Aldehyde condensations mediated by MgSO4 proceed in high yields (84-96%) when an excess of aldehyde is used. In contrast, only a slight excess of aldehyde (1.1 equiv) relative to tert-butanesulfinamide provides sulfinimines in high yields when the more Lewis acidic dehydrating agent CuSO4 is used. The CuSO4-mediated procedure is effective for a wide range of aldehydes, including sterically demanding aldehydes, such as isobutyraldehyde (90%), and electron-rich aldehydes, such as p-anisaldehyde (81%). The still more Lewis acidic Ti(OEt)(4) and Ti(O-i-Pr)(4) also afford N-tert-butanesulfinyl aldimines from especially unreactive aldehydes, such as pivaldehyde (82%). In addition, Ti(OEt)(4) is effective for the condensation of I with ketones to afford a wide range of N-tert-butanesulfinyl ketimines in good yields (77-91%). For sulfinyl ketimines derived from methyl or n-alkyl phenyl ketones and methyl or n-alkyl isopropyl ketones, only the E isomer is detected by H-1 and C-13 NMR in CDCl3. For those cases where the difference in steric demand about the imine is very small, such as for 2-hexanone, high E/Z ratios are still observed (5:1).
• Asymmetric synthesis of pre-protected α,α-disubstituted amino acids from tert-butanesulfinyl ketimines
  作者：George Borg、Masao Chino、Jonathan A Ellman

  DOI：10.1016/s0040-4039(00)02300-5

  日期：2001.2

  method for the asymmetric synthesis of pre-protected α,α-disubstituted amino acids is described. 5-Methylfuryllithium is added into sulfinyl ketimines 1 in the presence of AlMe3 to afford the sulfinamides 2 in 75–97% yields and with diastereoselectivities ranging from 75:25 to 99:1. Subsequent oxidation with RuCl3/NaIO4 affords tert-butanesulfonyl (Bus)-protected α,α-disubstituted amino acids 3 in 62–69%

  描述了一种不对称合成预保护的α，α-二取代氨基酸的方法。5- Methylfuryllithium加入到亚硫酮亚胺1中阿尔梅的存在3，得到亚磺酰胺2在75-97％的产率和非对映选择性与范围从75:25至99：1。用的RuCl随后氧化3 /的NaIO 4，得到叔-butanesulfonyl（总线）保护的α，α-二取代的氨基酸3在62-69％的产率。总线保护的氨基酸容易形成酰胺键，此后可以用TfOH / CH 2 Cl 2除去总线基团，得到游离胺。