(2S)-(+)-2-cyclohexyl-1-propanal | 62393-68-4

• 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: (2S)-(+)-2-cyclohexyl-1-propanal
• 英文别名: (S)-2-cyclohexyl-propionaldehyde；(S)-2-Cyclohexyl-propionaldehyd；(2S)-2-cyclohexylpropanal
• CAS: 62393-68-4
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: UQURIQWAEZGLAC-MRVPVSSYSA-N

物化性质

• 沸点：
  203.0±9.0 °C(Predicted)
• 密度：
  0.899±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  (2S)-(+)-2-cyclohexyl-1-propanal 在 水 、 铬酸 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以88%的产率得到(S)-2-Cyclohexylpropanoic 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：

  (S)-2-Cyclohexylpropanoic acid 在 chromium(VI) oxide 、 lithium aluminium tetrahydride 、 乙醚 作用下， 生成 (2S)-(+)-2-cyclohexyl-1-propanal
  参考文献：
  名称：

  Studies in Stereochemistry. XX. Steric Control of Asymmetric Induction in the Preparation of the 3-Cyclohexyl-2-butanol System¹

  摘要：

  DOI：

  10.1021/ja01119a067

文献信息

• Diastereofacial selectivity in the aldol reactions of chiral α-methyl aldehydes: a computer modelling approach.
  作者：Cesare Gennari、Siegfried Vieth、Angiolina Comotti、Anna Vulpetti、Jonathan M. Goodman、Ian Paterson

  DOI：10.1016/s0040-4020(01)80452-x

  日期：1992.1

  Transition state modelling of the aldol reaction of Z enol borinates with chiral α-methyl aldehydes (see Schemes 4 and 6) suggests that three transition structures (F, AF, R) play a dominant role in controlling π-facial selectivity. The “Felkin” structure (F) is characterized by Me-CH---C(O)-C* and CH---C(O)-C*-Me dihedral angles of about −60°/−65° and +100°. The “Roush” structure (R) has values of

  Z烯醇硼酸酯与手性α-甲基醛的醛醇缩合反应的过渡态模型（参见方案4和6）表明，三个过渡结构（F，AF，R）在控制π面选择性中起主要作用。“ Felkin”结构（F）的特征在于Me-CH --- C（O）-C *和CH --- C（O）-C * -Me二面角约为-60°/ -65°， + 100°。“劳斯（Roush）”结构（R）的值为-60°/ -65°和±175°/ 180°，而“反细致”结构（AF）的值为+ 60°/ + 65°和大约+ 50°。我们的分析表明，在与Z烯酸酯反应中，非键合相互作用在确定醛非对映选择性方面起着最重要的作用，立体电子效应可能会被空间效应所取代。与醛轴承相对小和反应“平坦的”的取代基（PH-，H 2 CCH-中，Me 2 CCH-）是3,4-顺式选择性（“Felkin”选择性），而与醛轴承笨重团的反应（各种烷基）是3，4-抗选择性的（“ Anti-Felk
• Enhanced Cram selectivity in carbonyl alkylation via‘naked’ anions and anti-Cram selectivity via‘naked’ cuprates
  作者：Yoshinori Yamamoto、Koshin Matsuoka

  DOI：10.1039/c39870000923

  日期：——

  Enhanced Cram selectivity is observed via the reaction of aldehydes (1) with ‘naked’ anions (2) prepared in situ from RM and Bu4NBr, while anti-Cram selectivity results from the reaction of (1) with ‘naked’ cuprates (4) prepared in situ from R2CuLi and Bu4NBr.

  通过醛（1）与由RM和Bu 4 NBr原位制备的'裸'阴离子（2）反应，可以观察到Cram选择性的提高，而（1）与'裸'的铜酸盐的反应产生了抗Cram选择性。4）由R 2 CuLi和Bu 4 NBr原位制备。
• 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。
• Hepatitis C inhibitor tri-peptides
  申请人：BOEHRINGER INGELHEIM (CANADA) LTD.

  公开号：EP2028186A2

  公开（公告）日：2009-02-25

  Racemates, diastereoisomers and optical isomers of a compound of formula (I): wherein B is H, a C6 or C10 aryl, C7-16 aralkyl; Het or (lower alkyl)-Het, all of which optionally substituted with C1-6 alkyl; C1-6 alkoxy; C1-6 alkanoyl; hydroxy; hydroxyalkyl; halo; haloalkyl; nitro; cyano; cyanoalkyl; amino optionally substituted with C1-6 alkyl; amido; or (lower alkyl)amide; or B is an acyl derivative of formula R4-C(O)-; a carboxyl of formula R4-O-C(O)-; an amide of formula R4-N(R5)-C(O)-; a thioamide of formula R4-N(R5)-C(S)-;or a sulfonyl of formula R4-SO2; R5 is H or C1-6 alkyl; and Y is H or C1-6 alkyl; R3 is C1-8 alkyl, C3-7 cycloalkyl, or C4-10 alkylcycloalkyl, all optionally substituted with hydroxy, C1-6 alkoxy, C1-6 thioalkyl, amido, (lower alkyl)amido, C6 or C10 aryl, or C7-16 aralkyl; R2 is CH2-R20, NH-R20, O-R20 or S-R20, wherein R20 is a saturated or unsaturated C3-7 cycloalkyl or C4-10 (alkylcycloalkyl), all of which being optionally mono-, di- or trisubstituted with R21, or R20 is a C6 or C10 aryl or C7-14 aralkyl optionally substituted, or R20 is Het or (lower alkyl)-Het, both optionally substituted, Het or (lower alkyl)-Het; carboxyl; carboxy(lower alkyl); C6 or C10 aryl, C7-14 aralkyl or Het, said aryl, aralkyl or Het being optionally substituted; and R1 is H; C1-6 alkyl, C3-7 cycloalkyl, C2-6 alkenyl, or C2-6 alkynyl, all optionally substituted with halogen; or a pharmaceutically acceptable salt or ester thereof.

  式 (I) 化合物的外消旋体、非对映异构体和光学异构体： 其中 B 是 H、C6 或 C10 芳基、C7-16 芳烷基、Het 或（低级烷基）-Het，所有这些都可选地被 C1-6 烷基、C1-6 烷氧基、C1-6 烷酰基、羟基、羟烷基、卤代、卤代烷基、硝基、氰基、氰基烷基、氨基、羟基烷基、卤代、卤代烷基、硝基、氰基、氰基烷基； 羟烷基；卤代；卤代烷基；硝基；氰基；氰基烷基；任选被 C1-6 烷基取代的氨基；氨基；或（低级烷基）酰胺；或 B 是式 R4-C(O)- 的酰基衍生物；式 R4-O-C(O)- 的羧基；式 R4-N(R5)-C(O)- 的酰胺；式 R4-N(R5)-C(S)- 的硫酰胺；或式 R4-SO2 的磺酰基。 Y 是 H 或 C1-6 烷基； R3 是 C1-8 烷基、C3-7 环烷基或 C4-10 烷基环烷基，均可任选被羟基、C1-6 烷氧基、C1-6 硫代烷基、氨基、（低级烷基）氨基、C6 或 C10 芳基或 C7-16 芳烷基取代； R2 是 CH2-R20、NH-R20、O-R20 或 S-R20，其中 R20 是饱和或不饱和的 C3-7 环烷基或 C4-10 （烷基环烷基），所有这些环烷基都可选择与 R21 进行单取代、二取代或三取代、 或 R20 是被任选取代的 C6 或 C10 芳基或 C7-14 芳烷基，或 R20 是 Het 或（低级烷基）-Het，两者均被任选取代，Het 或（低级烷基）-Het；羧基；羧基（低级烷基）；C6 或 C10 芳基、C7-14 芳烷基或 Het，所述芳基、芳烷基或 Het 被任选取代；以及 R1 是 H；C1-6 烷基、C3-7 环烷基、C2-6 烯基或 C2-6 烷炔基，均可任选被卤素取代；或其药学上可接受的盐或酯。
• Studies in Stereochemistry. XX. Steric Control of Asymmetric Induction in the Preparation of the 3-Cyclohexyl-2-butanol System¹
  作者：Donald J. Cram、Frederick D. Greene

  DOI：10.1021/ja01119a067

  日期：1953.12