THERMAL REARRANGEMENT OF ALLYL VINYL ETHER - HEAVY-ATOM KINETIC ISOTOPE EFFECTS AND THE TRANSITION STRUCTURE

被引：26

作者：

KUPCZYKSUBOTKOWSKA, L ^{[1
]}

SAUNDERS, WH ^{[1
]}

SHINE, HJ ^{[1
]}

SUBOTKOWSKI, W ^{[1
]}

机构：

[1] UNIV ROCHESTER,DEPT CHEM,ROCHESTER,NY 14627

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 14期

关键词：

D O I：

10.1021/ja00067a009

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Kinetic isotope effects (KIE) in the rearrangement of allyl vinyl ether (1, 3-oxa-1,5-hexadiene) to 4-pentenal (2) were measured for labeling with C-14 at the 2-, 4-, and 6-positions and with O-18 at the 3-position. BEBOVIB modeling calculations were applied successfully to the heavy-atom KIE and previously reported KIE for deuterium substitution at positions 4 and 6. From the calculations, it is deduced that the C4-O bond is 50-70% broken and the C1-C6 bond 10-30% formed in the transition structure. Further, there is strong coupling between the allyl and vinyloxy fragments, strong bonding within the allyl but relatively weak bonding within the vinyloxy fragment.

引用

页码：5957 / 5961

页数：5

共 20 条

[1]

CLAUSS K, 1962, LIEBIGS ANN CHEM, V654, P8

[2] SYNTHESIS AND CLAISEN REARRANGEMENT OF ALKOXYALLYL ENOL ETHERS - EVIDENCE FOR A DIPOLAR TRANSITION-STATE [J].