5,5-diphenyl-4-pentenoic acid | 5747-00-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,5-diphenyl-4-pentenoic acid
• 英文别名: 5,5-diphenylpent-4-enoic acid；γ,γ-Diphenyl-allyl-essigsaeure
• CAS: 5747-00-2
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: RSEHRYDTSSHDJN-UHFFFAOYSA-N

物化性质

• 熔点：
  82-83 °C(Solv: ligroine (8032-32-4))
• 沸点：
  160-170 °C(Press: 0.1 Torr)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-diphenyl-4-pentenoic acid 在 N,N'-羰基二咪唑 、 盐酸羟胺 作用下， 以 四氢呋喃 为溶剂， 反应 17.0h， 以88%的产率得到N-hydroxy-5,5-diphenylhex-4-enamide
  参考文献：
  名称：

  Stereodefined Access to Lactams via Olefin Difunctionalization: Iridium Nitrenoids as a Motif of LUMO-Controlled Dipoles

  摘要：

  Reported herein is a general platform of a stereodefined access to gamma-lactams via Cp*Ir-catalyzed olefin difunctionalization, where in situ generated Ir-nitrenoid is utilized as a key motif of 1,3-dipoles to enable amido transfer in a syn-selective manner. Computational studies suggested that the stereodefined process can be attributed to the proposed working mode of concerted [3 + 2] cyclization. Frontier molecular orbital (FMO) analysis implied that a low-lying lowest unoccupied molecular orbital (LUMO) of the Ir-imido fragment engages in the olefin interaction. Mechanistic understanding on the nitrene transfer process led us to develop mild catalytic protocols of stereoselective difunctionalization of alkenyl dioxazolones to furnish alpha-(haloalkyl)- or (oxyalkyl)lactam products which are of high synthetic and medicinal utility. Product stereochemistry (threo and erythro) was found to be designated by the olefin geometry (E/Z) of substrates.

  DOI：

  10.1021/jacs.9b04317
• 作为产物：
  描述：

  1,1-二苯基-1,5-戊二醇 在 potassium permanganate 、 苄基三丁基氯化铵 作用下， 以 水 、 甲苯 、 苯 为溶剂， 20.0~200.0 ℃ 、13.33 Pa 条件下， 反应 140.0h， 生成 5,5-diphenyl-4-pentenoic acid
  参考文献：
  名称：

  Lehmann, Jochen; Marquardt, Norbert, Liebigs Annalen der Chemie, 1988, p. 827 - 832

  摘要：

  DOI：

文献信息

• Pyridine compounds which are useful in treating a disease state
  申请人：Hoffman-La Roche Inc.

  公开号：US04927838A1

  公开（公告）日：1990-05-22

  The invention relates to compounds of the formula ##STR1## wherein Y and Y' are hydrogen or taken together are O or S, *A is paraphenylene or *----(CH.sub.2).sub.n --(X).sub.s --(CH.sub.2).sub.r ----, X is O, S or --CH.dbd.CH--, n or r, independently, are integers from 0 to 3, m is an integer from 0 to 1, s is an integer from 0 to 1, provided that when s is 1, n+m must be at least 2, t is an integer from 0 to 10, R.sub.1 and R.sub.2, independently, are lower alkyl, lower alkenyl or aryl, or one of R.sub.1 or R.sub.2 is hydrogen and the other is ##STR2## wherein W is ##STR3## --CH.sub.2 --CH.sub.2 --, --CH.sub.2 --, O, S, or ##STR4## and X.sub.1 is lower alkyl, phenyl unsubstituted or mono-, di- or trisubstituted by lower alkoxy, lower alkyl or halogen, and X.sub.2, X.sub.3 and X.sub.4, independently, are hydrogen, lower alkyl, lower alkoxy or halogen, R.sub.3 is hydrogen, lower alkyl or aryl, R.sub.4 is hydrogen, lower alkyl, aryl, aryl-lower alkyl or acyl, R.sub.5 is hydrogen or lower alkyl, R.sub.6 is hydrogen, lower alkyl, cycloalkyl, Het-lower alkyl or aryl, Het is a monocyclic 6-membered heteroaromatic radical containing one or two nitrogen atoms, which radical may be substituted by lower alkyl, halogen or aryl, and the asterisk denotes the point of attachment, and when R.sub.5 and R.sub.6 are different, their enantiomers and racemic mixtures thereof, when R.sub.1 and R.sub.2 are different, their geometric isomers, and pharmaceutically acceptable acid addition salts thereof.

  该发明涉及以下式的化合物##STR1##其中Y和Y'是氢或一起取O或S，*A是对苯二甲基或*----(CH.sub.2).sub.n --(X).sub.s --(CH.sub.2).sub.r ----，X是O、S或--CH.dbd.CH--，n或r独立地是0到3的整数，m是0到1的整数，s是0到1的整数，但当s为1时，n+m必须至少为2，t是0到10的整数，R.sub.1和R.sub.2独立地是较低的烷基、较低的烯烃基或芳基，或者R.sub.1或R.sub.2中的一个是氢，另一个是##STR2##其中W是##STR3##--CH.sub.2 --CH.sub.2 --，--CH.sub.2 --，O，S，或##STR4##，X.sub.1是较低的烷基，苯基未取代或被较低的烷氧基、较低的烷基或卤素单取代、双取代或三取代，X.sub.2、X.sub.3和X.sub.4独立地是氢、较低的烷基、较低的烷氧基或卤素，R.sub.3是氢、较低的烷基或芳基，R.sub.4是氢、较低的烷基、芳基、芳基-较低的烷基或酰基，R.sub.5是氢或较低的烷基，R.sub.6是氢、较低的烷基、环烷基、Het-较低的烷基或芳基，Het是含有一个或两个氮原子的单环6-成员杂芳基，该基团可以被较低的烷基、卤素或芳基取代，星号表示连接点，当R.sub.5和R.sub.6不同时，它们的对映异构体和外消旋混合物，当R.sub.1和R.sub.2不同时，它们的几何异构体，以及其药学上可接受的酸盐。
• Rate Constants for Anilidyl Radical Cyclization Reactions
  作者：E. Martinez、M. Newcomb

  DOI：10.1021/jo051953o

  日期：2006.1.1

  5-diphenyl-4-pentenamidyl radicals (3) were produced by 266 nm laser-flash photolysis of the corresponding N-(phenylthio) derivatives, and the rate constants for the cyclizations of these radicals were measured directly. The 5-exo cyclization reactions were fast (kc > 2 × 105 s-1), and radicals 3 generally behaved as electrophilic reactants with a Hammett correlation of ρ = 1.9 for five of the six radicals studied.

  通过相应N-（苯硫基）衍生物的266 nm激光快速光解法制得N-芳基-5,5-二苯基-4-戊烯基基团（3），并直接测量这些基团的环化速率常数。5-exo环化反应非常快（k c > 2×10 5 s - 1），对于所研究的六个自由基中的五个，自由基3通常表现为亲电子反应物，其Hammett相关性为ρ= 1.9。但是，对-甲氧基苯基取代的基团3f的环化速度比Hammett分析所预期的要快得多。母体自由基的可变温度研究3a（芳基=苯基）给出Arrhenius函数，log k = 9.2-4.4 / 2.3 RT（kcal / mol）。用于该反应的速率常数p乙基苯基取代anilidyl自由基3B与卜3 SNH在65℃下是ķ Ť = 4×10 5中号- 1个小号- 1。
• Enantioselective Oxidative Rearrangements with Chiral Hypervalent Iodine Reagents
  作者：Michael Brown、Ravi Kumar、Julia Rehbein、Thomas Wirth

  DOI：10.1002/chem.201504844

  日期：2016.3.14

  A stereoselective hypervalent iodine-promoted oxidative rearrangement of 1,1-disubstituted alkenes has been developed. This practically simple protocol provides access to enantioenriched α-arylated ketones without the use of transition metals from readily accessible alkenes.

  已经开发了立体选择性的高价碘促进的1，1-二取代的烯烃的氧化重排。这种实际上简单的方案无需使用易得的烯烃中的过渡金属即可提供对映体富集的α-芳基化酮。
• Small-Ring Compounds. XLVI. Stabilized Cyclopropylcarbinyl Anions. A Retro Cyclopropylcarbinyl-Allylcarbinyl Rearrangement¹
  作者：Adalbert Maercker、John D. Roberts

  DOI：10.1021/ja00960a031

  日期：1966.4

  The cyclopropylcarbinyl anion is stabilized by a phenyl group attached to the carbinyl carbon toward ring opening, provided that potassium or sodium is the counterion. Replacement of potassium by lithium or magnesium in ether leads to immediate rearrangement and formation of the corresponding covalent allylcarbinyl organometallic compound. These rearrangements are reversible as can be demonstrated

  环丙基羰基阴离子通过连接到羰基碳上的苯基向开环方向稳定，前提是钾或钠是抗衡离子。在醚中用锂或镁代替钾会导致立即重排并形成相应的共价烯丙基羰基有机金属化合物。这些重排是可逆的，正如二苯基环丙基-羰基锂所证明的那样，它在四氢呋喃中稳定，但在乙醚中完全打开为 y,y-二苯基烯丙基羰基锂。这种情况下的逆重排可以通过简单地向乙醚溶液中加入四氢呋喃来实现。y,y-二苯基烯丙基羰基溴化汞与钾的反应导致闭环，形成相应的环丙基羰基钾衍生物。
• Selenium-Catalyzed Regioselective Cyclization of Unsaturated Carboxylic Acids Using Hypervalent Iodine Oxidants
  作者：Fateh V. Singh、Thomas Wirth

  DOI：10.1021/ol202800k

  日期：2011.12.16

  A new and convenient selenium-catalyzed regioselective cyclization of γ,δ-unsaturated carboxylic acids to the corresponding 3,6-dihydro-2H-pyran-2-ones is described. The cyclization products have been obtained in good to excellent yields using diphenyl diselenide as a catalyst and [bis(trifluoroacetoxy)iodo]benzene as a stoichiometric oxidant.

  描述了一种新的和便捷的硒催化的γ，δ-不饱和羧酸向相应的3，6-二氢-2 H-吡喃-2-酮的区域选择性环化。使用二苯二硒化物作为催化剂和[双（三氟乙酰氧基）碘]苯作为化学计量的氧化剂，已经以良好或优异的收率获得了环化产物。