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lgq101木蟲 (小有名氣)
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[求助]
求翻譯(有機合成)!。~~謝謝
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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. |

| 二炔4a,b,d,在格拉布斯第一代催化劑和炔丙醇作用下發(fā)生[2 + 2 + 2] 環(huán)三聚化,與最初的液相結(jié)果比較該法的一個顯著差異是區(qū)域選擇性。盡管異二氫吲哚26a,d形成預(yù)期的區(qū)域選擇性產(chǎn)物,但有可靠的事實說明苯環(huán)取代降低了區(qū)域選擇性,我們再次假定這種不同是由固相反應(yīng)中芳基和聚苯乙烯基之間的相互作用所致。顯然,這種低區(qū)域選擇性在這種特定情況下是有利的,因為它為那些通過液相反應(yīng)不能有效接受像26b這樣的小分子的物質(zhì)提供了通道。 |

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