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lgq101木虫 (小有名气)
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[求助]
求翻译（有机合成）！！！~~~谢谢
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| In the [2 + 2 + 2] cyclotrimerization (36–38) of diynes 4a,b,d using Grubbs’ first-generation catalyst and propargyl alcohol (39), one significant difference in regioselectivity was noted in comparison to our original solution-phase results. While isoindolines 26a,d were formed in the expected regioselectivities (26a, 100∶0; 26d/26′d, 50∶50), the corresponding phenyl-substituted product 26b/26′b was formed in significantly lower regioselectivity on solid support (67∶33 vs. 91∶9).We again postulate that this difference may result from interactions of this aromatic substrate with the polystyrene matrix in the solid-phase reaction. Notably, however, this decreased selectivity was advantageous in this particular context, because it afforded access to the minor regioi-somer 26′b that was not accessible in useful quantities via the solution-phase reaction. |
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【答案】应助回帖
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sltmac(金币+2): 感谢应助，欢迎常来本版~~ 2011-06-29 18:18:51
lgq101(金币+15, 翻译EPI+1): 谢谢~~~~~~~ 2011-06-29 19:10:14
sltmac(金币+2): 感谢应助，欢迎常来本版~~ 2011-06-29 18:18:51
lgq101(金币+15, 翻译EPI+1): 谢谢~~~~~~~ 2011-06-29 19:10:14
| 二炔4a,b,d,在格拉布斯第一代催化剂和炔丙醇作用下发生[2 + 2 + 2] 环三聚化，与最初的液相结果比较该法的一个显著差异是区域选择性。尽管异二氢吲哚26a,d形成预期的区域选择性产物，但有可靠的事实说明苯环取代降低了区域选择性，我们再次假定这种不同是由固相反应中芳基和聚苯乙烯基之间的相互作用所致。显然，这种低区域选择性在这种特定情况下是有利的，因为它为那些通过液相反应不能有效接受像26b这样的小分子的物质提供了通道。 |
2楼2011-06-29 12:21:13
