(S)-4-(1-methylethyl)-3-<(E)-2-oxobut-2-enyl>-5,5-diphenyloxazolidin-2-one | 218800-35-2

• 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: (S)-4-(1-methylethyl)-3-<(E)-2-oxobut-2-enyl>-5,5-diphenyloxazolidin-2-one
• 英文别名: (S)-4-(1-methylethyl)-3-[(E)-1-oxobut-2-enyl]-5,5-diphenyloxazolidin-2-one；(S,E)-3-but-2-enoyl-4-isopropyl-5,5-diphenyloxazolidin-2-one；(4S)-3-[(E)-but-2-enoyl]-5,5-diphenyl-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 218800-35-2
• 化学式: C₂₂H₂₃NO₃
• 分子量: 349.43
• InChiKey: GQCQUHINOLGYKN-FZBXERKRSA-N

物化性质

• 沸点：
  455.3±55.0 °C(Predicted)
• 密度：
  1.149±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-4-(1-methylethyl)-3-<(E)-2-oxobut-2-enyl>-5,5-diphenyloxazolidin-2-one 在 六甲基磷酰三胺 、 sodium hexamethyldisilazane 、 四氯化锡 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  乙酸酯型乙烯基乙烯酮甲硅烷基N，O-缩醛的远程不对称感应

  摘要：

  通过使用具有手性助剂的乙酸酯型乙烯基乙烯酮甲硅烷基N，O-缩醛，通过乙烯基类Mukaiyama aldol反应实现了远程不对称诱导。通过用SnCl 4和BF 3 ·OEt 2处理，分别从巴豆酸酯和1-缬氨酸衍生的甲硅烷基N，O-乙缩醛选择性地提供了O-甲硅烷基化的5 R-和5 S-加合物。发现了SnCl 4介导的甲硅烷基二烯醇醚的异构化，并且所得的主要异构体显示出高反应性，从而以高的立体选择性得到γ-加合物。

  DOI：

  10.1021/acs.orglett.6b03476
• 作为产物：
  描述：

  (S)-4-(1-methylethyl)-3-<(R)-2-methyl-1-oxo-3-phenylpropyl>-5,5-diphenyloxazolidin-2-one 在 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 生成 (S)-4-(1-methylethyl)-3-<(E)-2-oxobut-2-enyl>-5,5-diphenyloxazolidin-2-one
  参考文献：
  名称：

  A Useful Modification of theEvans Auxiliary: 4-Isopropyl-5,5-diphenyloxazolidin-2-one

  摘要：

  The 4-isopropyl-5,5-diphenyloxazolidinone (1) is readily prepared from (R)- or (S)-valine ester, PhMgBr, and ethyl chlorocarbonate. It has a melting point of ca. 250 degrees, a low solubility in most organic solvents, and a C=O group which is sterically protected from nucleophilic attack. Thus; the soluble N-acyl-oxazolidinones (7-16) can be prepared from 1 with BuLi at temperatures around 0 degrees instead of - 78 degrees (Scheme 3): their Li enolates can be generated with BuLi, rather than with LDA, and deacylation in the final step of the procedure can be achieved with NaOH at ambient temperatures (Scheme 12),with facile recovery of the precipitating auxiliary 1 (filtering, washing, and drying). The following reactions of N-acyl-oxazolidinones from 1 have been investigated: alkylations (Scheme 4), aminomethylations and hydroxymethylations (Scheme 5), aldol additions (Schemes 6 and 7), Michael additions (Schemes 9 and 10), and a (4 + 2) cycloaddition (Scheme II). The well-known features of reactions following the Evans methodology (yield, diastereoselectivity, dependence on conditions, counter ions, additives etc.) prevail in these transformations. Most products, however, have higher melting points and a much more pronounced crystallization tendency than those derived from conventional oxazolidinones, and can thus be purified by recrystallization, avoiding chromatography (Table 1). The disadvantage of 1 having a higher molecular weight (ca. 150 Da) than the non-phenyl-substituted auxiliary is more than compensated by the ease of its application, especially on large scale. A number of crystal structures of oxazolidinones derived from 1 and a TICl4 complex of an oxazolidinone are described and discussed in view of the diastereoselective-reaction mechanisms.

  DOI：

  10.1002/(sici)1522-2675(19981111)81:11<2093::aid-hlca2093>3.0.co;2-x

文献信息

• Applications of the Chiral Auxiliaries DIOZ and TRIOZ for Conjugate Additions and Comparison with Other Auxiliaries
  作者：Hanspeter Sprecher、Stefan Pletscher、Manuel Möri、Roger Marti、Christoph Gaul、Krystyna Patora-Komisarska、Ekatarina Otchertianova、Albert K. Beck、Dieter Seebach

  DOI：10.1002/hlca.200900385

  日期：2010.1

  prepared and used for conjugate additions of organocuprate reagents (Me, iPr, Ph, 4‐MeOPh) in the β‐carbonyl (Table 2) and in the α‐carbonyl position (NO2‐derivative 11 in Scheme 3). The yields and diastereoselectivities are compared with previously tested enoyl‐oxazolidinones (Table 2). Highest diastereoselectivities (>90%) are always observed with the 4‐Ph derivatives (Hruby effect). Nitroacryloyl‐oxazolidinones

  许多ñ -丙烯酰基，Ñ -crotonoyl-，ñ - （3,3,3- trifluorocrotonoyl） - ，Ñ -cinnamoyl-，和ñ - （3- nitroacryloyl）-4-异丙基或-4-苯基唑烷-2-酮与偕二苯基取代，即，7 - 15，已被制备并用于有机铜试剂的共轭加成（Me中，我PR，pH值，4-MeOPh）在β -羰基（表2），并在的α -羰基位置（NO 2 -衍生物11在方案3中）。将产率和非对映选择性与先前测试的烯酰基-恶唑烷酮（表2）进行比较。使用4-Ph衍生物总是观察到最高的非对映选择性（> 90％）（Hruby效应）。硝基丙烯酰基-恶唑烷酮和相应的苯薄荷醇酯的非对映选择性加成较少（方案3）。还测试了由3-（1-甲基乙基）-5,5-二苯基恶唑烷二-2-酮（DIOZ）衍生的Li 2-烯酸酯-亚硝酸盐的α-羰基烷基化反应（方案4）。描述了三种丙烯酰基-恶唑
• Synthesis of Silyloxy Dienes by Silylene Transfer to Divinyl Ketones: Application to the Asymmetric Synthesis of Substituted Cyclohexanes
  作者：Christian C. Ventocilla、K. A. Woerpel

  DOI：10.1021/jo202650k

  日期：2012.4.6

  to divinyl ketones provided 2-silyloxy-1,3-dienes with control of stereochemistry and regioselectivity. The products participated in Diels–Alder reactions with electron-deficient alkenes and imines to form six-membered-ring products diastereoselectively. Cycloaddition reactions with alkenes bearing chiral auxiliaries provided access to chiral, nonracemic cyclohexenes. The methodology, therefore, represents

  银催化的亚甲硅基转移到二乙烯基酮，提供了具有立体化学和区域选择性控制的 2-甲硅烷氧基-1,3-二烯。该产物参与与缺电子烯烃和亚胺的狄尔斯-阿尔德反应，非对映选择性地形成六元环产物。与带有手性助剂的烯烃的环加成反应提供了获得手性非外消旋环己烯的途径。因此，该方法代表在单个烧瓶中合成非对映体和对映体纯产物。高度取代的环己烯产物可以在碳-硅键氧化后进行立体选择性官能化以提供环己醇。
• Crystal Structures– AManifesto for the Superiority of the Valine-Derived 5,5-Diphenyloxazolidinone as an Auxiliary in Enantioselective Organic Synthesis
  作者：Christoph Gaul、Bernd W. Schweizer、Paul Seiler、Dieter Seebach

  DOI：10.1002/1522-2675(200206)85:6<1546::aid-hlca1546>3.0.co;2-2

  日期：2002.6

  The crystal structures of 32 derivatives of 4-isopropyl-5,5-diplienyl-1,3-oxazolidin-2-one (A and 1 - 31) are presented (Fig. 2 and Tables 1-3). In all but four structures, the Me2CH group is in a disposition that mimick a Me3C group (Figs. 3-5). The five-membered ring shows conformations from an envelope form with the Ph2C group out of the plane containing the other four atoms to the twist form with the twofold axis through the C=O group (Fig. 6, and Table 2). In the entire series, the Me2CH and the neighboring trans Ph group are approximately antiperiplanar (average torsion angle 155degrees). The structural features are used to interpret the previously observed reactivity behavior of the diphenyl-oxazolidinone derivatives. The practical advantages of the title compound over classical Evans auxiliaries are outlined (Figs. I and 7 and Scheme 2): high crystallinity of all derivatives, steric protection of the C=O group in the ring, excellent stereoselectivities in reactions of its derivatives, and safe preparation and easy recovery of the auxiliary.
• Remote Asymmetric Induction Using Acetate-Type Vinylketene Silyl <i>N</i>,<i>O</i>-Acetals
  作者：Naoya Sagawa、Haruka Sato、Seijiro Hosokawa

  DOI：10.1021/acs.orglett.6b03476

  日期：2017.1.6

  Remote asymmetric induction by the vinylogous Mukaiyama aldol reaction using the acetate-type vinylketene silyl N,O-acetal possessing a chiral auxiliary has been achieved. The silyl N,O-acetal derived from crotonate and l-valine afforded the O-silylated 5R- and 5S-adducts selectively by treatment with SnCl4 and BF3·OEt2, respectively. The SnCl4-mediated isomerization of silyl dienol ether was found

  通过使用具有手性助剂的乙酸酯型乙烯基乙烯酮甲硅烷基N，O-缩醛，通过乙烯基类Mukaiyama aldol反应实现了远程不对称诱导。通过用SnCl 4和BF 3 ·OEt 2处理，分别从巴豆酸酯和1-缬氨酸衍生的甲硅烷基N，O-乙缩醛选择性地提供了O-甲硅烷基化的5 R-和5 S-加合物。发现了SnCl 4介导的甲硅烷基二烯醇醚的异构化，并且所得的主要异构体显示出高反应性，从而以高的立体选择性得到γ-加合物。
• A Useful Modification of theEvans Auxiliary: 4-Isopropyl-5,5-diphenyloxazolidin-2-one
  作者：Tobias Hintermann、Dieter Seebach

  DOI：10.1002/(sici)1522-2675(19981111)81:11<2093::aid-hlca2093>3.0.co;2-x

  日期：1998.11.11

  The 4-isopropyl-5,5-diphenyloxazolidinone (1) is readily prepared from (R)- or (S)-valine ester, PhMgBr, and ethyl chlorocarbonate. It has a melting point of ca. 250 degrees, a low solubility in most organic solvents, and a C=O group which is sterically protected from nucleophilic attack. Thus; the soluble N-acyl-oxazolidinones (7-16) can be prepared from 1 with BuLi at temperatures around 0 degrees instead of - 78 degrees (Scheme 3): their Li enolates can be generated with BuLi, rather than with LDA, and deacylation in the final step of the procedure can be achieved with NaOH at ambient temperatures (Scheme 12),with facile recovery of the precipitating auxiliary 1 (filtering, washing, and drying). The following reactions of N-acyl-oxazolidinones from 1 have been investigated: alkylations (Scheme 4), aminomethylations and hydroxymethylations (Scheme 5), aldol additions (Schemes 6 and 7), Michael additions (Schemes 9 and 10), and a (4 + 2) cycloaddition (Scheme II). The well-known features of reactions following the Evans methodology (yield, diastereoselectivity, dependence on conditions, counter ions, additives etc.) prevail in these transformations. Most products, however, have higher melting points and a much more pronounced crystallization tendency than those derived from conventional oxazolidinones, and can thus be purified by recrystallization, avoiding chromatography (Table 1). The disadvantage of 1 having a higher molecular weight (ca. 150 Da) than the non-phenyl-substituted auxiliary is more than compensated by the ease of its application, especially on large scale. A number of crystal structures of oxazolidinones derived from 1 and a TICl4 complex of an oxazolidinone are described and discussed in view of the diastereoselective-reaction mechanisms.