环戊酮,2-戊基-,(S)- | 133338-07-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 环戊酮,2-戊基-,(S)-
• 英文名称: (S)-2-n-pentylcyclopentanone
• 英文别名: (2S)-2-pentylcyclopentanone；(S)-2-pentylcyclopentanone；(R,S)-2-Pentyl-cyclopentanone；(2S)-2-pentylcyclopentan-1-one
• CAS: 133338-07-5
• 化学式: C₁₀H₁₈O
• 分子量: 154.252
• InChiKey: VNWOJVJCRAHBJJ-VIFPVBQESA-N

物化性质

• 沸点：
  217.7±8.0 °C(Predicted)
• 密度：
  0.895±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  环戊酮,2-戊基-,(S)- 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到(S)-(-)-delta-癸内酯
  参考文献：
  名称：

  Asymmetric Hydrogenation of Olefins with Aprotic Oxygen Functionalities Catalyzed by BINAP-Ru(II) Complexes

  摘要：

  Cyclic alpha,beta-unsaturated ketones, alkylidene lactones, and alkenyl ethers have been hydrogenated in high enantiomeric excesses by use of BINAP-Ru(II) complexes (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) as catalysts. 2-Alkylidenecyclopentanones were hydrogenated in the presence of [RuCl(BINAP)(benzene)]Cl, Ru2Cl4(BINAP)2(NEt(3)), or Ru(OCO CH3 )(2)(BINAP) in up to 98% ee, while in the case of 2-benzylidene- and 2-(3-phenylpropylidene)cyclopentanones, enantiomeric excesses of the hydrogenation were below 50% under the same conditions. The sense of asymmetric induction as well as the enantioselectivity (95% ee) obtained in the hydrogenation of (E)-2-propylidene-gamma-butyrolactone were the same as those of the (Z)-isomer. Lactones, 2- and 4-alkylidene-gamma-butyrolactones, were converted to the corresponding saturated gamma-butyrolactones in 95% ee. Hydrogenation of diketene with the catalytic system derived from {RuCl[(S)-BINAP](benzene)}Cl and triethylamine or complex Ru2Cl4[(S)-BINAP](2)(NEt(3)) established a new synthetic route to (R)-4-methyl-2-oxetanone, a promising monomer of biodegradable polymers, in up to 97% selectivity and 92% ee. Alkenyl ethers, 2-methylenetetrahydrofuran, and 2-methyl-3,4-dihydrofuran have also been hydrogenated to give 2-methyltetrahydrofuran in 91 and 87% ee, respectively.

  DOI：

  10.1021/jo00107a014
• 作为产物：
  描述：

  dipentylzinc 在 叔丁基锂 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 正戊烷 为溶剂， 反应 67.0h， 生成 环戊酮,2-戊基-,(S)-
  参考文献：
  名称：

  高对映体过量的光学活性α-取代酮的实用合成

  摘要：

  光学活性 α-取代酮的高度对映选择性合成可以通过使用涉及在 CuCN·2LiCl 存在下立体选择性反 S N 2'-烯丙基取代的反应序列，然后使用 B 氧化中间体环烯基锂物质来实现(MeO) 3 /NaBO 3 ·4H 2 O。取代反应以完美的手性转移进行。

  DOI：

  10.1055/s-2007-965887

文献信息

• Effects of Lithium Salts on the Enantioselectivity of Protonation of Enolates with Chiral Imide
  作者：Akira Yanagisawa、Tetsuo Kikuchi、Hisashi Yamamoto

  DOI：10.1055/s-1998-1594

  日期：1998.2

  An increase in enantioselectivity was observed in the asymmetric protonation of prochiral enolates with a chiral imide using lithium salt as an additive. For example, (R)-enriched 2-n-pentylcyclopentanone 6 was obtained in high yield with 90% ee when the silyl enol ether 4 was treated with n-BuLi in the presence of 5 equiv of LiBr in Et2O and the resulting lithium enolate 5 was then protonated by a solution of (S,S)-imide 1 in THF. In contrast, the product 6 obtained without LiBr exhibited a lower enantiomeric excess (74% ee)

  在使用手性亚胺进行非手性烯醇盐的不对称质子化反应中，加入锂盐作为添加剂可观察到对映选择性的提高。例如，当硅醚烯醇4在乙醚中与n-BuLi和等量的LiBr反应，所得锂烯醇盐5再与(S,S)-亚胺1的THF溶液进行质子化时，可高收率获得(R)-富集的2-正戊基环戊酮6，其对映体过量达到90%。相比之下，未加LiBr时获得的产物6对映体过量较低，仅为74% ee。
• Asymmetric hydrogenation of unsaturated carbonyl compounds catalyzed by BINAP-Ru(II) complexes. Enantioselective synthesis of γ-butyrolactones and cyclopentanones
  作者：Tetsuo Ohta、Tsutomu Miyake、Nobuo Seido、Hidenori Kumobayashi、Susumu Akutagawa、Hidemasa Takaya

  DOI：10.1016/s0040-4039(00)92330-x

  日期：1992.1

  Asymmetric hydrogenation of 2- and 4-alkylidene-γ-butyrolactones and 2-alkylidenecyclopentanones catalyzed by BINAP—Ru(II) complexes affords the corresponding γ-butyrolactones and cyclopentanones in 94–98% ee. Hydrogenation of (E)- and (Z)-2-propylidene-γ-butyrolactone catalyzed by the same catalyst gave the products with the same absolute configuration and in almost equal enantioselectivities, which

  BINAP-Ru（II）配合物催化2-和4-亚烷基-γ-丁内酯和2-亚烷基环戊酮的不对称加氢，可得到94-98％ee的相应γ-丁内酯和环戊酮。在同一催化剂下催化的（E）-和（Z）-2-亚丙基-γ-丁内酯的加氢反应得到的产物具有相同的绝对构型和几乎相等的对映选择性，这表明烯烃的几何形状不会影响立体化学和对映选择性。
• Enoyl acyl carrier protein reductase (FabI) catalyzed asymmetric reduction of the CC double bond of α,β-unsaturated ketones: preparation of (R)-2-alkyl-cyclopentanones
  作者：Ji Liu、Jinchuan Wu、Zhi Li

  DOI：10.1039/c4cc04150j

  日期：——

  Enoyl-ACP reductase (FabI) was identified as a non-OYE 'ene'-reductase for asymmetric reduction of the C=C double bond of alpha, beta-unsaturated ketones. Reduction of several 2-alkylidenecyclopentanones with A-FabI and E-FabI gave (R)-2-alkylcyclopentanones in 95-90% and 70-81% ee, respectively. The product ee was improved to 99-98% in high yield by subsequent one-pot biooxidation.

  烯丙基ACP还原酶（FabI）被鉴定为非OYE'烯'还原酶，用于不对称还原α，β-不饱和酮的C = C双键。用A-FabI和E-FabI还原几种2-亚烷基环戊酮，分别得到95-90％和70-81％ee的（R）-2-烷基环戊酮。通过随后的一锅式生物氧化，产物ee以高产率提高至99-98％。
• Enantioselective protonation of prochiral enolates with chiral imides
  作者：Akira Yanagisawa、Tetsuo Kikuchi、Takeshi Kuribayashi、Hisashi Yamamoto

  DOI：10.1016/s0040-4020(98)00482-7

  日期：1998.8

  New chiral proton sources possessing an asymmetric 2-oxazoline ring, (S,S)-imide 1 and related imides, were synthesized from Kemp's triacid and optically active 2-amino alcohols. With these chiral imides, various lithium enolates of α-monoalkylated cycloalkanones were effectively protonated with excellent to moderate enantioselectivity. An increase in enantioselectivity was observed in the asymmetric

  由肯普氏三酸和旋光性2-氨基醇合成了具有不对称2-恶唑啉环，（S，S）-酰亚胺1和相关酰亚胺的新手性质子源。使用这些手性酰亚胺，可以以优异的中度对映选择性有效地质子化α-单烷基化环烷酮的各种烯醇锂。使用锂盐作为添加剂，在用（S，S）-酰亚胺1制备的手性烯醇盐的不对称质子化中，观察到对映选择性的增加。例如，当甲硅烷基烯醇醚时，以90％ee以高收率获得了富含（R）的2-正戊基环戊酮35在5当量的LiBr在Et 2 O中存在下，用n- BuLi处理33，然后通过（S，S）-酰亚胺1在THF中的溶液使所得的烯醇锂34质子化。相反，在没有LiBr的情况下获得的产物35表现出较低的对映体过量（74％ee）。
• Novozyme 435 Asymmetric Hydrolysis of Enol Ester with Series Acid Moiety
  作者：Quan Li、Weimin Jia、Zhijian Wang、Xiaodan Guo

  DOI：10.14233/ajchem.2014.16200

  日期：——

  (R)-2-pentylcyclopentanone can be synthesized by the asymmetric hydrolysis of enol esters, catalyzed by immobilized candida antarctica (novozyme 435) lipase. Different acid moieties influence the stereoselectivity of lipase. Enol esters can be prepared from anhydrides and 2-pentylcyclopentanone. When introducing optical (S)-(+)-2-methyl-butyric acid, the hydrolysis of optical enol ester showed great enhancement of the specific rotation compared to the racemic enol ester, the specific rotation of product raise from [a]25D-10° (c 0.1, CH3OH) to [a]25D-72° (c 0.1, CH3OH). However, when bringing chiral acid moity, the specific rotation still can not catch up with the value compared to the isobutyric moiety. The specific rotation of (R)-2-pentylcyclopentanone is [a]25D-102.20° (c 0.1, CH3OH), the optimum temperature and pH were 30 °C and 6.5, respectively. Then 81.06 % ee of (R)-d-decalactone was prepared by the Baeyer-Villiger oxidation of (R)-2-pentylcyclopentanone.

  (R)-2-戊基环戊酮可以通过固定化南极假丝酵母 (novozyme 435) 脂肪酶催化烯醇酯的不对称水解来合成。不同的酸部分影响脂肪酶的立体选择性。烯醇酯可由酸酐和2-戊基环戊酮制备。当引入光学(S)-(+)-2-甲基-丁酸时，光学烯醇酯的水解比外消旋烯醇酯表现出比旋光度大大增强，产物的比旋光度从[a]25D-升高10°（c 0.1，CH3OH）至[a]25D-72°（c 0.1，CH3OH）。然而，当引入手性酸部分时，与异丁酸部分相比，比旋光度仍然无法赶上该值。 (R)-2-戊基环戊酮的比旋光度为[a]25D-102.20°(c 0.1,CH3OH)，最适温度和pH分别为30℃和6.5。然后通过(R)-2-戊基环戊酮的Baeyer-Villiger氧化制备81.06％ee的(R)-d-癸内酯。