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para ‐Selective Benzylation of Aryl Iodides by the in situ Preparation of ArIF 2 : a Hypervalent Iodine‐Guided Electrophilic Substitution
Author(s) -
Noorollah Jennifer,
Im Haram,
Siddiqi Fatima,
Singh Nirvanie,
Spatola Nicholas R.,
Chaudhry Azka,
Jones Taro J.,
Hyatt I. F. Dempsey
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000393
Subject(s) - hypervalent molecule , chemistry , electrophile , aryl , iodine , iodide , transmetalation , borylation , combinatorial chemistry , electrophilic substitution , lewis acids and bases , organic chemistry , alkyl , catalysis
Hypervalent iodine‐guided electrophilic substitution (HIGES) was described previously for the para ‐selective benzylation of aryl‐λ 3 ‐iodane diacetates. One drawback of the method was the synthesis and isolation of hypervalent iodine starting materials. An improvement is reported herein in which the benzylation product can be afforded from an aryl iodide via an in situ oxidation. The metal‐like properties of hypervalent iodine have been demonstrated in the transmetallation of metalloid groups such as silicon and boron and are compatible with multiple Lewis acid activators. A desirable facet of both the previous method and the newly reported procedure is that the iodine atom is incorporated into the product thus providing greater atom economy and a valuable functional group handle for further transformations. The following communication contributes to other articles in the field that imply there is a general HIGES mechanism yet to be fully understood.