Development of a general, sequential, ring-closing metathesis/intramolecular cross-coupling reaction for the synthesis of polyunsaturated macrolactones.
Development of a general, sequential, ring-closing metathesis/intramolecular cross-coupling reaction for the synthesis of polyunsaturated macrolactones.
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DOI：
10.1021/ja1047363
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发表时间：
2010-08-25
影响因子：
15
通讯作者：
Muhuhi, Joseck M.
中科院分区：
文献类型：
--
作者：
Denmark, Scott E.;Muhuhi, Joseck M.
本文介绍了一种合成含共轭Z，Z-1，3-二烯亚基的大环内酯的一般策略。该策略的核心是一个连续的闭环复分解，形成一个不饱和的硅氧烷环，然后与侧链烯基碘分子内交叉偶联反应。各种前体的高度模块化组装允许制备含有11-、12-、13-和14-元环的不饱和大环内酯。尽管闭环复分解过程顺利进行，但分子内交叉偶联需要对钯源、溶剂、氟化物源和特别是氟化物水合水平进行广泛优化。在最佳条件下（包括注射泵高稀释），大环内酯以53-78%的产率作为单一立体异构体产生。用同样的方法合成了一种含有E，Z-1，3-二烯单元的苯并稠合12元环大环内酯。通过九氟丁磺酸芳基酯与乙烯基三甲基硅烷的新型Heck反应，然后用ICl碘脱硅制备E-2-苯乙烯基碘。
A general strategy for the construction of macrocyclic lactones containing conjugated Z,Z-1,3-diene subunits has been is described. The centerpiece of the strategy is a sequential ring-closing metathesis that forms an unsaturated siloxane ring followed by an intramolecular cross-coupling reaction with a pendant alkenyl iodide. A highly modular assembly of the various precursors allowed the preparation of unsaturated macrolactones containing 11-, 12-, 13- and 14-membered rings. Although the ring closing metathesis process proceeded uneventfully, the intramolecular cross-coupling required extensive optimization of palladium source, solvent, fluoride source and particularly fluoride hydration level. Under the optimal conditions (including syringe pump high dilution), the macrolactones were produced in 53-78% yield as single stereoisomers. A benzo fused 12-membered ring macrolactone containing an E,Z-1,3-diene unit was also prepared by the same general strategy. The E-2-styryl iodide was prepared by a novel Heck reaction of an aryl nonaflate with vinyltrimethylsilane followed by iododesilylation with ICl.
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影响因子：
2.3
作者：
ANDREINI, BP;DELLAMICO, DB;PELIZZI, G
通讯作者：
PELIZZI, G
影响因子：
15
作者：
Denmark SE;Liu JH;Muhuhi JM
通讯作者：
Muhuhi JM
影响因子：
5.2
作者：
Denmark, SE;Sweis, RF
通讯作者：
Sweis, RF
影响因子：
15
作者：
BAZAN, GC;OSKAM, JH;SCHROCK, RR
通讯作者：
SCHROCK, RR
影响因子：
3.6
作者：
Denmark, SE;Kobayashi, T
通讯作者：
Kobayashi, T