3-(Penten-5-yl)-2(1H)-piperidinone | 155193-62-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-(Penten-5-yl)-2(1H)-piperidinone
• 英文别名: 3-(4-penten-1-yl)-2-piperidinone；3-(4'-pentenyl)piperidin-2-one；3-pent-4-enyl-piperidine-2-one；(pent-4-enyl)piperidin-2-one；3-pent-4-enylpiperidin-2-one；3-(Pent-4-enyl)2-piperidone；3-(4-Pentenyl)-2-piperidinone
• CAS: 155193-62-7
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: WGNSWBMFWGQTPU-UHFFFAOYSA-N

物化性质

• 沸点：
  306.8±11.0 °C(Predicted)
• 密度：
  0.923±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(Penten-5-yl)-2(1H)-piperidinone 在 dirhodium tetraacetate 三乙基硅烷 、 三氟化硼乙醚 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 二氯甲烷 、 乙腈 、 xylene 、 苯 为溶剂， 反应 11.42h， 生成 2-Acetyl-2-hydroxy-2,5,6,7,8,9,10,10a-octahydro-1H-pyrido<3,2,1-ij>quinolin-3-one
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035
• 作为产物：
  描述：

  哌啶酮 、 5-溴-1-戊烯 以92%的产率得到3-(Penten-5-yl)-2(1H)-piperidinone
  参考文献：
  名称：

  Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles

  摘要：

  一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下，用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现，这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时，最初形成的N-酰基亚胺离子会快速失去质子，产生S,N-酮烯醇缩醛，比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果，这是分子内反应的立体化学产物的成因。分子力学计算表明，内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反，高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。

  DOI：

  10.1055/s-1994-25621

文献信息

• Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles
  作者：Albert Padwa、Scott R. Harring、Donald L. Hertzog、William R. Nadler

  DOI：10.1055/s-1994-25621

  日期：——

  A series of α,α-disubstituted thioisomünchnones were prepared by treating acyclic or cyclic thioamides with bromoacetyl chloride in the presence of triethylamine. The resulting mesoionic dipole was found to undergo bimolecular 1,3-dipolar cycloaddition with several different dipolarophiles. When a hydrogen atom is present in the α-position of the thioamide, the initially formed N-acyl iminium ion undergoes proton loss to produce a S,N-ketene acetal at a faster rate than thioisomünchnone formation. The cycloaddition behavior of several substituted thioisomünchnones which possess a tethered alkene were also examined. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring π-bond across the transient thioisomünchnone dipole. Molecular mechanics calculations reveal that the endo diastereomers are significantly lower in energy than the corresponding exo isomers. Attempts to cycloadd the thioisomünchnone dipole across a tethered indolyl ring were unsuccessful. Instead, products derived by nucleophilic cyclization of the indolyl ring onto the thio N-acyl iminium ion were formed in good yield.

  一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下，用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现，这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时，最初形成的N-酰基亚胺离子会快速失去质子，产生S,N-酮烯醇缩醛，比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果，这是分子内反应的立体化学产物的成因。分子力学计算表明，内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反，高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。
• On the Intramolecular 1,4-Dipolar Cycloaddition Reaction of Thiazinium Betaines for the Construction of Aza-, Diaza-, and Polyaza-Heterocyclic Ring Systems
  作者：Albert Padwa、Steven J. Coats、Scott R. Harring、Lazaros Hadjiarapoglou、Mark A. Semones

  DOI：10.1055/s-1995-4032

  日期：1995.8

  A series of bicyclic anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides containing tethered π-systems are easily prepared from the reaction of thiolactams with 1,3-bielectrophiles. These cross-conjugated heteroaromatic betaines undergo regio- and stereospecific 1,4-dipolar cycloaddition in good yield to produce cycloadducts containing a carbonyl sulfide bridge which can be induced to lose COS on further heating. Two of the cycloadducts were characterized by single crystal X-ray determinations. Control of ring size in the final product of the cycloaddition can be achieved by variation of the dipolarophilic chain length. Entry to the [6,6,5]- and [6,6,6]pyridone ring systems was possible using phenylalkynyl-substituted thioamides. Intramolecular 1,4-dipolar cycloaddition of a thiazinium betaine dipole also occurs across an indolyl π-bond. With only one substituent group in the 9-position of the bicyclic betaine, the reaction takes an entirely different course unless a highly activated π-bond is incorporated into the tether. The preferred reaction with modestly activated π-systems corresponds to loss of the activated proton to produce an S,N-ketene acetal. When a ketene S,S-acetal group was incorporated onto the side chain, the 1,4-dipolar cycloaddition reaction was facilitated relative to proton loss.

  一系列含有联接π系统的双环无水-4-羟基-2-氧-1,3-噻唑鎓氢氧化物可以通过硫内酰胺与1,3-双电亲体的反应轻松制备。这些交错共轭的杂芳香族贝塔因在良好的产率下经历区域性和立体特异性的1,4-偶极环加成，生成含有羰基硫桥的环加成物，在进一步加热时可以诱导失去COS。通过单晶X射线测定对其中两个环加成物进行了表征。通过改变偶极亲核链的长度，可以控制环加成反应最终产物的环大小。使用苯基炔基取代的硫氨基可以实现对[6,6,5]-和[6,6,6]吡啶酮环系的导入。噻唑鎓贝塔因偶极的环内1,4-偶极环加成也发生在吲哚的π键上。在双环贝塔因的9位仅有一个取代基时，反应的路径会完全不同，除非在连结中加入一个高度活化的π键。与适度活化的π系统的优选反应对应于活化质子的失去，从而生成S,N-烯酮缩醛。当在侧链上引入烯酮S,S-缩醛基时，相较于质子失去，1,4-偶极环加成反应得以促进。
• Conjugate addition of amides to α,β-unsaturated esters by CsF-Si(OEt)4 system
  作者：Kyo Han Ahn、Seok Jong Lee

  DOI：10.1016/s0040-4039(00)73184-4

  日期：1994.3

  The conjugate addition of amides to α,β-unsaturated esters proceeds efficiently with an equimolar amount of Si(OEt)4 and a catalytic amount of CsF to afford the corresponding N-substituted amides.

  用等摩尔量的Si（OEt）4和催化量的CsF有效地将酰胺共轭加到α，β-不饱和酯上，得到相应的N-取代的酰胺。
• Diastereo- and Enantioselective Intramolecular [2+2] Photocycloaddition Reactions of 3-(ω′-Alkenyl)- and 3-(ω′-Alkenyloxy)-Substituted 5,6-Dihydro-1<i>H</i>-pyridin-2-ones
  作者：Dominik Albrecht、Florian Vogt、Thorsten Bach

  DOI：10.1002/chem.200902616

  日期：2010.4.12

  37 % overall yield from 3‐diazopiperidin‐2‐one (15) by an α,α‐chloroselenylation reaction at the 3‐position followed by nucleophilic displacement of a chloride ion with an ω‐alkenolate and oxidative elimination of selenoxide. Upon irradiation at λ=254 nm, the precursor compounds underwent a clean intramolecular [2+2] photocycloaddition reaction. Substrates 2 and 5, tethered by a two‐atom chain, exclusively

  3-（ω' -烯基） -取代的5,6-二氢- 1 H ^ -吡啶-2-酮2 - 4制备为前体光环通过从3-碘-5,6-二氢-1-交叉耦合ħ -吡啶-2-酮（8）或-更优选-从相应的α-（ω' -烯基） -取代的δ-戊内酰胺9 - 11由硒化/消除序列（56-62％总产率）。3-（ω'-链烯氧基）-取代的5,6-二氢-1 H-吡啶2-2-酮5和6可从3-重氮哌啶-2-酮的总产率中获得43％和37％（15）通过在3位的α，α-氯硒基化反应，然后用ω-链烯酸酯进行氯离子的亲核置换并氧化消除亚硒酸盐。在λ＝ 254nm处照射时，前体化合物进行了干净的分子内[2 + 2]光环加成反应。基板2和5，由两个原子的链拴，排他地输送的相应交叉产品19和20，和基片3，5，和6，通过拴系更长的链，得到直制品21 - 23。完全的区域和非对映选择性光环加成反应的产率为63-83％。在手性模板（−）- 1和（+）‐
• Generation of the Dihydro-5H-Thiazolo[3,2-a]pyridin-3-one Ring System by Proton Loss from Isothiomünchnones
  作者：Albert Padwa、Zhijia J. Zhang

  DOI：10.3987/com-93-s32

  日期：——

  Dihydro-5H-thiazolo[3,2-a]pyridin-3-ones are easily generated by proton loss from isothiomunchnones. The closely related tetrahydro-2H-pyrido[2,1-b]-[1,3]thiazin-4-one ring system was prepared by treating piperidine-2-thione with acryloyl chloride. These cyclic S,N-ketene acetals undergo smooth reaction with different electrophiles in the presence of Lewis acids.