Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups
Halo-Jacobsen Rearrangement Induced by Steric Repulsion between peri-Iodo Groups
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DOI：
10.1021/acs.joc.3c00165
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发表时间：
2023-06-02
影响因子：
3.6
通讯作者：
Nishiwaki, Nagatoshi
中科院分区：
文献类型：
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作者：
Iwai, Kento;Nishiguchi, Noa;Nishiwaki, Nagatoshi
萘环由于邻位碘基间的空间排斥而变形。1，8-二碘萘与三氟甲磺酸发生卤代-Jacobsen重排反应，生成1，5-二碘萘和1，4-二碘萘。在该反应中，酸诱导的脱卤均偶联反应也可生成4，4 '-二碘-1，1'-联萘，反应选择性可通过改变反应温度来控制。DFT计算和一些对照实验表明，这些化合物是通过不同的途径形成的。
The naphthalene ring is distorted due to steric repulsionbetweeniodo groups at the peri-positions. Due to the distortion,1,8-diiodonaphthalene underwent a halo-Jacobsen rearrangement whentreated with trifluoromethanesulfonic acid, producing 1,5-diiodonaphthaleneand 1,4-diiodonaphthalene. In this reaction, acid-induced dehalogenativehomocoupling also proceeded to form 4,4 '-diiodo-1,1 '-binaphthyl.The reaction selectivity could be controlled by varying the reactiontemperature. DFT calculations and some control experiments revealedthat these compounds were formed by different pathways.