(S)-2,3,3-trimethylbutanal | 76094-60-5

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (S)-2,3,3-trimethylbutanal
• 英文别名: (2S)-2,3,3-trimethylbutanal
• CAS: 76094-60-5
• 化学式: C₇H₁₄O
• 分子量: 114.188
• InChiKey: IHZLWFWSVIGUST-ZCFIWIBFSA-N

物化性质

• 沸点：
  130.0±9.0 °C(Predicted)
• 密度：
  0.805±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-2,3,3-trimethylbutanal 在 水 、 铬酸 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以82%的产率得到(S)-2,3,3-trimethylbutanoic acid
  参考文献：
  名称：

  Chiral synthesis via organoboranes. 30. Facile synthesis, by the Matteson asymmetric homologation procedure, of .alpha.-methyl boronic acids not available from asymmetric hydroboration and their conversion into the corresponding aldehydes, ketones, carboxylic acids, and amines of high enantiomeric purity

  摘要：

  2-(alpha-Methylalkyl)- or 2-(alpha-arylethyl)-1,3,2-dioxaborinanes, RMeHC*BO2(CH2)3 (R = alkyl or aryl), of very high enantiomeric purity, not available from asymmetric hydroboration, can be prepared by the Matteson asymmetric homologation procedure of optically pure pinanediol or 2,3-butanediol boronate esters with (dichloromethyl)lithium, LiCHCl2, conveniently generated in situ in THF at -78-degrees-C, followed by reaction with either a Grignard reagent or an alkyllithium, with subsequent removal of the chiral auxiliaries. alpha-Methyl boronic esters thus obtained are readily converted into the corresponding aldehydes by the reaction with [methoxy(phenylthio)methyl]lithium [LiCH(OMe)SPh] (MPML) and mercuric chloride, followed by oxidation with hydrogen peroxide in a pH 8 buffer medium. The two-phase aqueous chromic acid procedure can be used to oxidize these aldehydes to the corresponding alpha-methyl carboxylic acids of very high enantiomeric purity without significant racemization. Additionally, pinanediol or 2,3-butanediol alpha-methylorganylboronate esters can be conveniently converted into borinic ester derivatives, RMeHC*BMe(OMe), of very high enantiomeric purity by reaction with methyllithium, followed by treatment with methanolic hydrogen chloride and subsequent recovery of the valuable chiral auxiliaries. These borinic ester derivatives are converted into alpha-methyl ketones and alpha-methyl primary amines of known absolute configuration by the alpha,alpha-dichloromethyl methyl ether (DCME) reaction and the reaction with hydroxylamine-O-sulfonic acid, respectively. The present synthesis of chiral 2-organyl-1,3,2-dioxaborinanes by the Matteson route, together with our direct asymmetric hydroboration procedure, makes it possible to synthesize many chiral boronic acid derivatives in very high enantiomeric purities. These complementary procedures greatly expand the scope of asymmetric synthesis via chiral organoboranes.

  DOI：

  10.1021/jo00010a022
• 作为产物：
  描述：

  3,3-二甲基丁酰氯 在 palladium on activated charcoal 、 正丁基锂 、 二甲基乙基硅烷 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (S)-2,3,3-trimethylbutanal
  参考文献：
  名称：

  On the Constitutional Stability ofη1-Allylmetal Compounds

  摘要：

  Many eta(1)-allymetal species undergo a rapid haptotropic rearrangement. The stereochemical outcome of reactions of these allylmetal species with aldehydes depends on whether the haptotropic rearrangement is faster or slower than the reaction with the aldehyde. We present here a test system based on kinetic resolution, by which just this information becomes available. Thus, haptotropic rearrangement of cyclohexenyllithium, -magnesium chloride, -titanium triisopropoxide, and -titanium tetraisopropoxide, was found to be faster than addition to the aldehyde 9. Borotropic rearrangement in cyclohexenyldiethylborane was found to be slower than the addition to the aldehyde 9.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1724::aid-chem1724>3.0.co;2-e

文献信息

• A Very Mild and Chemoselective Oxidation of Alcohols to Carbonyl Compounds
  作者：Lidia De Luca、Giampaolo Giacomelli、Andrea Porcheddu

  DOI：10.1021/ol016501m

  日期：2001.9.1

  oxidation of primary alcohols and beta-amino alcohols to the corresponding aldehydes and alpha-amino aldehydes can be carried out at room temperature and in methylene chloride, using trichloroisocyanuric acid in the presence of catalytic TEMPO: aliphatic, benzylic, and allylic alcohols, and beta-amino alcohols are rapidly oxidized without no overoxidation to carboxylic acids. Secondary carbinols are slowly

  伯醇和β-氨基醇可在室温下和在二氯甲烷中使用三氯异氰尿酸在TEMPO催化下高效氧化为相应的醛和α-氨基醛：脂族，苄基和烯丙基醇，以及β-氨基醇被迅速氧化而不会过度氧化成羧酸。仲甲醇被缓慢氧化，因此反应具有高度的化学选择性。反应：见文字。
• Tetrahydrofuro[3,2-b] pyrrol-3-one intermediates
  申请人：Quibell Martin

  公开号：US20090192322A1

  公开（公告）日：2009-07-30

  The present invention relates to a process for preparing a compound of formula (Ia), (Ib), (Ic) or (Id), or a pharmaceutically acceptable salt, hydrate, solvate, complex or prodrug thereof, said process comprising the steps of: (A) (i) treating a compound of formula (IVa), where R 48 is alkyl or tosyl, with an oxidising agent to form a compound of formula (Va); and (ii) converting said compound of formula (Va) to a compound of formula (Ia) or (Ic); or (B) (i) treating a compound of formula (IVb), where R 48 is alkyl or tosyl, with an oxidising agent to form a compound of formula (Vb); and (ii) converting said compound of formula (Vb) to a compound of formula (Ib) or (Id).

  本发明涉及一种制备式(Ia)、(Ib)、(Ic)或(Id)化合物或其药学上可接受的盐、水合物、溶剂合物、复合物或前药的方法，该方法包括以下步骤：(A) (i)用氧化剂处理式(IVa)化合物，其中R48是烷基或甲苯磺酰基，以形成式(Va)化合物；(ii)将所述式(Va)化合物转化为式(Ia)或(Ic)化合物；或(B) (i)用氧化剂处理式(IVb)化合物，其中R48是烷基或甲苯磺酰基，以形成式(Vb)化合物；(ii)将所述式(Vb)化合物转化为式(Ib)或(Id)化合物。
• Brinkmann, Heinrich; Hoffmann, Reinhard W., Chemische Berichte, 1990, vol. 123, # 12, p. 2395 - 2401
  作者：Brinkmann, Heinrich、Hoffmann, Reinhard W.

  DOI：——

  日期：——
• EP1730142B1
  申请人：——

  公开号：EP1730142B1

  公开（公告）日：2011-06-29
• PEPTIDOMIMETIC COMPOUNDS AND ANTIBODY-DRUG CONJUGATES THEREOF
  申请人：Lee Ho Huat

  公开号：US20160279261A1

  公开（公告）日：2016-09-29

  This invention relates to peptidomimetic linkers and anti-body drug conjugates thereof, to pharmaceutical compositions containing them, and to their use in therapy for the prevention or treatment of cancer.