Highly stereoselective synthesis of bicyclo[n.3.0]alkanes by titanium tetrachloride promoted [3+2] cycloaddition of allylsilanes and 1-acetylcycloalkenes

被引:43
作者
Knolker, HJ
Foitzik, N
Goesmann, H
Graf, R
Jones, PG
Wanzl, G
机构
[1] UNIV KARLSRUHE,INST ANORGAN CHEM,D-76128 KARLSRUHE,GERMANY
[2] TECH UNIV CAROLO WILHELMINA BRAUNSCHWEIG,INST ANORGAN & ANALYT CHEM,D-38106 BRAUNSCHWEIG,GERMANY
关键词
allylsilanes; diastereoselective synthesis; bicycloalkanes; cycloadditions; enones;
D O I
10.1002/chem.19970030409
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The titanium tetrachloride promoted reaction of allylsilanes 1 with 1-acetylcyclohexene is shown to afford the silylbicyclo[4.3.0]nonanes 9 ([3+2] cyclo-addition products) along with the 1-acetyl-2-allylcyclohexane 4 (Hosomi-Sakurai product). Here we report that systematic variation of the substituents at the silicon atom of 1 allows suppression of the classical Hosomi-Sakurai reaction in favor of the [3+2] cycloaddition. Cycloaddition of the allylsilanes 1d, 1i, and 1k with 1-acetylcycloalkenes 10, containing a 5-, 6-, 7-, 8-, or 12-membered ring, gives rise to the corresponding silylbicyclo[n.3.0]alkanes 11-13. The cycloaddition of allyltriisopropylsilane (1k) and 1-acetyl-2-methylcycloalkenes 15 provides silylbicyclo[n.3.0]alkanes 16 with two contiguous quaternary carbon centers. The stereochemistry of the silylbicyclo[n.3.0]alkanes 11 a-c and 14 is unambiguously determined by X-ray analysis and C-13 NMR spectroscopy.
引用
收藏
页码:538 / 551
页数:14
相关论文
共 96 条
[1]   STEREOSELECTIVE CONSTRUCTION OF TETRAHYDROFURAN BY TIN-(IV)-CHLORIDE PROMOTED [3+2]-CYCLOADDITION OF ALLYLSILANE TO ALPHA-KETO ESTER [J].
AKIYAMA, T ;
ISHIKAWA, K ;
OZAKI, S .
CHEMISTRY LETTERS, 1994, (03) :627-630
[2]   ASYMMETRIC-SYNTHESIS OF TETRAHYDROFURANS BY DIASTEREOSELECTIVE [3+2]-CYCLOADDITION OF ALLYLSILANES WITH ALPHA-KETO ESTERS BEARING AN OPTICALLY-ACTIVE CYCLITOL AS A CHIRAL AUXILIARY [J].
AKIYAMA, T ;
YASUSA, T ;
ISHIKAWA, K ;
OZAKI, S .
TETRAHEDRON LETTERS, 1994, 35 (45) :8401-8404
[3]   FORMAL [3+3]-CYCLOADDITIONS AND [3+2]-CYCLOADDITIONS OF ALLYLSILANES WITH BENZYLIC CATIONS [J].
ANGLE, SR ;
BOYCE, JP .
TETRAHEDRON LETTERS, 1994, 35 (35) :6461-6464
[4]   RULES FOR RING-CLOSURE [J].
BALDWIN, JE .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1976, (18) :734-736
[5]   REACTION OF LITHIUM ACETYLIDE ETHYLENEDIAMINE WITH KETONES [J].
BEUMEL, OF ;
HARRIS, RF .
JOURNAL OF ORGANIC CHEMISTRY, 1964, 29 (07) :1872-&
[6]   STEREOCHEMISTRY OF THE SAKURAI REACTION - ADDITIONS TO CYCLOHEXENONES AND CYCLOHEPTENONES [J].
BLUMENKOPF, TA ;
HEATHCOCK, CH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (08) :2354-2358
[7]  
Chan D. M. T., 1991, COMPREHENSIVE ORGANI, V3, P271
[8]  
COLVIN E, 1981, SILICON ORGANIC SYNT, P19
[9]   MECHANISM OF SOLVOLYSIS OF (2-BROMOETHYL)TRIMETHYLSILANE - EVIDENCE FOR MIGRATION OF TRIMETHYLSILYL GROUP [J].
COOK, MA ;
EABORN, C ;
WALTON, DRM .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1970, 24 (02) :301-&
[10]  
CORRIU RJP, 1970, J CHEM SOC CHEM COMM, P213