STEREOSELECTIVE SYNTHESIS OF ALPHA,BETA-TRANS-SPIRO-BETA-LACTONES BY DIELS-ALDER CYCLOADDITION OF 1,3-DIENES TO ALPHA-METHYLENE-BETA-LACTONE AND THEIR DECARBOXYLATION BY PYROLYSIS TO (E)-ALKYLIDENECYCLOALKENES, A CONVENIENT OLEFINATION METHOD

被引:14
作者
ADAM, W [1 ]
SALGADO, VON [1 ]
PETERS, EM [1 ]
PETERS, K [1 ]
VONSCHNERING, HG [1 ]
机构
[1] MAX PLANCK INST FESTKORPERFORSCH,W-7000 STUTTGART,GERMANY
来源
CHEMISCHE BERICHTE-RECUEIL | 1993年 / 126卷 / 06期
关键词
STEREOSELECTIVITY; DIELS-ALDER REACTION; BETA-LACTONE; ALPHA-METHYLENE; SPIROLACTONES; ALKYLIDENE CYCLOALKENES; DECARBOXYLATION;
D O I
10.1002/cber.19931260632
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A number of spiro-beta-lactones was prepared in good to excellent yields through stereoselective [4 + 2] cycloaddition of beta-isopropyl-alpha-methylene-beta-lactone (1) with acyclic, cyclic, heterocyclic and aromatic 1,3-dienes by sealed-tube reaction at moderate temperatures (50 - 130-degrees-C). Flash pyrolysis of the resulting spiro-beta-lactones 2 in the gas phase at 400-degrees-C afforded by decarboxylation exclusively the corresponding (E)-isopropylidenealkenes in high yields with retention of the initial geometry and without double bond isomerization. This olefination method constitutes an excellent stereoselective synthesis of (E)-alkylidenecycloalkenes.
引用
收藏
页码:1481 / 1486
页数:6
相关论文
共 31 条
  • [1] ALPHA-METHYLENE-BETA-LACTONE, A NOVEL HETEROCYCLIC RING-SYSTEM VIA DEOXYGENATION OF ALPHA-METHYLENE-BETA-PEROXYLACTONES WITH TRIPHENYLPHOSPHANE
    ADAM, W
    HASEMANN, L
    PRECHTL, F
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1988, 27 (11) : 1536 - 1537
  • [2] ALPHA-METHYLENE BETA-LACTONES AS MASKED ALLENES AND ALLENE EQUIVALENTS - SOME SELECTED CHEMICAL-TRANSFORMATIONS
    ADAM, W
    ALBERT, R
    HASEMANN, L
    SALGADO, VON
    NESTLER, B
    PETERS, EM
    PETERS, K
    PRECHTL, F
    VONSCHNERING, HG
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (20) : 5782 - 5785
  • [3] ALPHA-METHYLENE-BETA-LACTONES AS NOVEL ALLENE EQUIVALENTS - REGIOSELECTIVE [4+2]-CYCLOADDITION AND STEREOSELECTIVE DECARBOXYLATION FOR THE INTRODUCTION OF EXO-ALKYLIDENE FUNCTIONALITIES
    ADAM, W
    HASEMANN, L
    [J]. TETRAHEDRON LETTERS, 1991, 32 (48) : 7033 - 7036
  • [4] ALPHA-METHYLENE BETA-S-THIOLACTONES - SYNTHESIS OF A NEW HETEROCYCLE BY SULFURIZATION OF AN ALPHA-METHYLENE BETA-LACTONE AND ITS STRUCTURE
    ADAM, W
    HASEMANN, L
    [J]. CHEMISCHE BERICHTE, 1990, 123 (06) : 1449 - 1451
  • [5] STEREOSPECIFIC INTRODUCTION OF DOUBLE-BONDS VIA THERMOLYSIS OF BETA-LACTONES
    ADAM, W
    BAEZA, J
    LIU, J
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (06) : 2000 - &
  • [6] SYNTHESIS OF ALPHA-METHYLENE BETA-LACTONES, NOVEL HETEROCYCLES
    ADAM, W
    ALBERT, R
    GRAU, ND
    HASEMANN, L
    NESTLER, B
    PETERS, EM
    PETERS, K
    PRECHTL, F
    VONSCHNERING, HG
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (20) : 5778 - 5781
  • [7] Examinations into the process of diene synthesis.
    Alder, K
    Stein, G
    [J]. ANGEWANDTE CHEMIE, 1937, 50 : 0510 - 0519
  • [8] [Anonymous], 1988, ANGEW CHEM, V100, P1594
  • [9] BATTISTE MA, 1983, SYNTHESIS-STUTTGART, P493
  • [10] VERSATILE ALLENE AND CARBON-DIOXIDE EQUIVALENTS FOR DIELS-ALDER REACTION
    BONJOUKLIAN, R
    RUDEN, RA
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (25) : 4095 - 4103