Stereochemistry of the thermal isomerizations of trans-1-ethenyl-2-phenylcyclopropane to 4-phenylcyclopentene

被引：23

作者：

Baldwin, JE

Bonacorsi, SJ

机构：

[1] Department of Chemistry, Syracuse University, Syracuse

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1996年 / 118卷 / 35期

关键词：

D O I：

10.1021/ja9613771

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The stereochemical course of the thermal isomerization of trans-1-ethenyl-2-phenylcyclopropane to 4-phenylcyclopentene at 216.4 degrees C in the gas phase has been uncovered through syntheses and kinetic studies based on chiral d(9)-labeled analogs. This example of the vinylcyclopropane-to-cyclopentene rearrangement takes place with the participation of all four stereochemically distinct paths, the relative contributions (+/-3%) being 58% si, 8% ar, 24% sr, and 10% al. The stereochemical outcome is determined by alternative diradical transition structures of comparable energy, rather than by orbital symmetry control.

引用

收藏

页码：8258 / 8265

页数：8

相关论文

共 50 条

[1]

Andrews G. D., 1976, J AM CHEM SOC, V98, P6705

[2] STRUCTURAL-ANALYSIS OF 4-PHENYLCYCLOPENTENE FROM NATURAL ABUNDANCE C-13 MAGNETIC-RESONANCE SHIELDINGS, MULTIPLICITIES, AND COUPLING-CONSTANTS [J].

ANDRIST, AH ;

KALYNCHUK, DG .

SPECTROSCOPY LETTERS, 1978, 11 (02) :133-142

[3] CATALYTIC ASYMMETRIC-SYNTHESIS OF CYCLOPROPANE-CARBOXYLIC ACIDS - AN APPLICATION OF CHIRAL COPPER CARBENOID REACTION [J].

ARATANI, T .

PURE AND APPLIED CHEMISTRY, 1985, 57 (12) :1839-1844

[4] ABSOLUTE CONFIGURATION OF CIS-2-PHENYLCYCLOPROPANE-CARBOXYLIC ACID AND RELATED COMPOUNDS [J].

ARATANI, T ;

NAKANISI, Y ;

NOZAKI, H .

TETRAHEDRON, 1970, 26 (07) :1675-&

[5] STEREOCHEMISTRY OF THE THERMAL ISOMERIZATIONS OF (1S,2R)-1-(E-STYRYL)-2-PHENYLCYCLOPROPANE TO 3,4-DIPHENYLCYCLOPENTENES [J].

ASUNCION, LA ;

BALDWIN, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (43) :10672-10677

[6]

ASUNCION LA, 1996, J ORG CHEM, V60, P5778

[7] STEREOCHEMISTRY OF THE THERMAL-ISOMERIZATION OF VINYLCYCLOPROPANE TO CYCLOPENTENE [J].

BALDWIN, JE ;

VILLARICA, KA ;

FREEDBERG, DI ;

ANET, FAL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (23) :10845-10846

[8] STEREOCHEMISTRY OF THE THERMAL ISOMERIZATIONS OF (1R,2S)-1-(E-1-PROPENYL)-2-PHENYLCYCLOPROPANE TO 3-METHYL-4-PHENYLCYCLOPENTENES [J].

BALDWIN, JE ;

BONACORSI, S .

JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (24) :7401-7409

[9] COMPLETE KINETIC-ANALYSIS OF THE THERMAL STEREO-MUTATIONS OF (+)-(1S,2S,3R)-RHO-1-CYANO-TERT-2-METHYL-1,2,TERT-3-TRIDEUTERIO-CYCLOPROPANE [J].

BALDWIN, JE ;

CARTER, CG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (05) :1362-1368

[10] STEREOCHEMISTRY OF THE THERMAL ISOMERIZATIONS OF (1R,2R)-1-((E)-STYRYL)-2-METHYLCYCLOPROPANE TO 3-PHENYL-4-METHYLCYCLOPENTENES [J].

BALDWIN, JE ;

BONACORSI, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (23) :10621-10627

← 1 2 3 4 5 →