| 134111-64-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• CAS: 134111-64-1；134176-00-4；134176-01-5；134176-02-6；136779-21-0；136779-22-1
• 化学式: C₁₅H₁₅NO₂
• 分子量: 241.29
• InChiKey: NKUWGLYSYMCYKM-OGCHJJRDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  37.38
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  N-苯基马来酰亚胺 、 2,3-戊二烯 以 氘代甲苯 为溶剂， 以32%的产率得到
  参考文献：
  名称：

  Stereochemical features of the (2 + 2) cycloaddition reactions of chiral allenes. 2. Cycloaddition of enantioenriched 1,3-dimethylallene with the 1,2-disubstituted alkenes N-phenylmaleimide and dimethyl fumarate

  摘要：

  The cycloaddition reaction of N-phenylmaleimide (NPMI) with an excess of enantioenriched 1,3-dimethylallene (13DMA) has been carried out with varying initial enantiomeric excesses (ee's) of the 13DMA and differing concentrations of the reactants. The recovered unreacted 13DMA showed no loss in ee. The four cycloadducts have been separated by HPLC, and their ee's have been determined by the use of a chiral NMR chemical shift reagent. Two of the cycloadducts have retained approximately 80% of the ee of the starting 13DMA, one approximately 50%, and the fourth approximately 10%. Molecular modeling calculations have been carried out on the conformational energy surface for the approach of reactant models to the activated complexes for diradical intermediate formation, and on models for the diradical intermediates. A mechanism is proposed for the formation of the diradical intermediates and the cycloadducts involving three separate minimum-energy reaction channels for the formation of specific conformations of the diradical intermediates which undergo ring closure to specific cycloadducts. These minimum-energy reaction channels differ in the extent of the facial selectivity of attack on the NPMI during the irreversible formation of the diradical intermediates. The cycloaddition of 13DMA with dimethyl fumarate (DMFM) produces two major cycloadducts which have been formed involving > 96 and > 70% transfer of the ee of the starting 13DMA. Two very minor cycloadducts are also formed, one possessing approximately 74% of the ee of the starting 13DMA with the other minor cycloadduct being formed in such small quantities that is isolation and measurement of its ee could not be accomplished. Molecular modeling calculations have been carried out on the conformational energy surface of the two reactants in approaching the activated complexes for diradical intermediate formation and on the conformational preferences of the diradical intermediates. The detailed stereochemical analysis of the formation of the cycloadducts suggests that there are two major minimum-energy reaction channels involved in diradical intermediate and cycloadduct formation arising from the same low-energy conformation for approach of the reactants to two different activated complexes and diradical intermediates.

  DOI：

  10.1021/jo00021a047

文献信息

• Cycloaddition reactions of 1,3-dimethylallene. Assignment of stereochemistry of the cycloadducts and interpretation of product distributions
  作者：Daniel J. Pasto、Kiyoaki D. Sugi、James L. Malandra

  DOI：10.1021/jo00012a007

  日期：1991.6

  The structures of the cycloadducts formed in the (2 + 2) cycloaddition reactions of 1,3-dimethylallene (13DMA) with 1,1-dichloro-2,2-difluoroethene (1122), acrylonitrile (ACN), methyl acrylate (MAC), N-phenylmaleimide (NPMI), and diethyl fumarate (DEF) and maleate (DEM) and the product distributions have been interpreted on the basis of favored conformations for diradical formation and ring closure to the cycloadducts. The stereochemistry of the ring substitution in the cycloadducts derived from ACN and MAC has been assigned on the basis of the relative chemical shifts of H-2, the relative magnitudes of the vicinal coupling constants between H-1 and H-2, the relative magnitudes of the cross-ring coupling constants between H-1 and H-3 and H-4, which are highly dependent on the conformations of the substituted methylenecyclobutane ring systems, and, in the case of the ACN cycloadducts, the results of NOE studies. The stereochemistry about the exocyclic double bonds in the cycloadducts derived from 13DMA with 1122, ACN, and MAC has been assigned on the basis of the relative magnitudes of the allylic and homoallylic coupling constants between H-1, H-3, and H-4 with H-5 and CH3b, the interpretation of which is based on the results of conformational studies carried out by molecular mechanics and ab initio MO calculations on methylenecyclobutane (28), pseudoaxial and pseudoequatorial 2-methyl-methylenecyclobutane (29a and 29e), ethylidenecyclobutane (30), and pseudoaxial and pseudoequatorial 2-methylethylidenecyclobutane (31a and 31e). The results of these calculations indicate that with 29 the pseudoaxial conformation 29a is significantly populated, while with 31 the pseudoaxial conformation 31a should be overwhelmingly populated. The trends in the relative chemical shifts and the magnitudes of the vicinal and long-range coupling constants observed in the NMR spectra of the cycloadducts derived from the reaction of 13DMA with NPMI and DEF have allowed for the assignment of the stereochemistry about the exocyclic double bonds and the ring substitution of the cycloadducts formed in these reactions. The product distributions formed in the cycloaddition reactions of 13DMA with ACN and NPMI have been analyzed by molecular mechanics calculations on the conformational preferences for formation of the diradical intermediates and on the conformational preferences of the diradical intermediates which lead directly to cycloadduct formation. The predictions of the molecular mechanics calculations are in agreement with the observed configurations in the cycloadducts formed from (R)-(-)-13DMA and ACN and consistent with the observed product distributions. Detailed analyses of the observed product distributions in the cycloaddition reactions of 13DMA with the various radicophiles lead to the conclusions that in the cycloaddition reaction with 1122 the anti,anti diradical intermediate is preferentially formed, while in the cycloadditions reactions with ACN, MAC, and NPMI the anti,syn diradical intermediates are preferentially formed. The differences in stereochemical preferences are discussed in terms of possible differences in the degree of development of the transition states for diradical intermediate formation with different dominant steric interactions.The cycloaddition with DEM produces only trans diester products and also results in the isomerization of DEM to DEF. These data imply the reversible formation of the diradical intermediates from DEF and DEM, as well as internal rotation occurring competitive with ring closure.