Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes**

Zhang, Xin1,2; Liu, Liu Leo1,2

2022-02-01

10.1002/anie.202116658

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Lewis bases are well known to stabilize electron-deficient species. We demonstrate herein that the redox property of a monocoordinated aluminylene 1 featuring only four valence electrons for the shell of Al can be boosted by a Lewis base. The coordination of 1 with an N-heterocyclic carbene (NHC) effectively shrinks the HOMO-LUMO gap, thereby enhancing the reactivity of the ensuing acyclic mono-NHC-stabilized aluminylene 2, which is isoelectronic with singlet carbenes. Moreover, such base coordination completely reverses the predominant chemical reactivity (i.e. electrophilicity/nucleophilicity) of aluminylenes. In marked contrast to 1, 2 readily undergoes a [4+1] cycloaddition reaction with naphthalene and biphenylene at room temperature. Strikingly, the enhanced ambiphilic nature of Al in 2 also enables facile cleavage of aromatic C-C bonds of inert arenes in both intra- and intermolecular fashion affording 3 and 5. The formation of 5 represents the first example of the cleavage of an aromatic C(3)-C(4) bond in biphenylene by a single-atom center.

Aluminylene Ambiphilicity Arenes Frontier Orbitals Small-Molecule Activation

SCI ; EI

英语

NI期刊

第一 ; 通讯

National Natural Science Foundation of China[22101114] ; Department of Education of Guangdong Province[2021KQNCX079] ; SUSTech startup fund[Y01216248]

Chemistry

Chemistry, Multidisciplinary

WOS:000750671200001

WILEY-V C H VERLAG GMBH

20220611603125

Aluminum ; Cycloaddition

Aluminum:541.1 ; Chemical Reactions:802.2 ; Organic Compounds:804.1

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China

Zhang, Xin,Liu, Liu Leo. Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes**[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2022,61.

Zhang, Xin,&Liu, Liu Leo.(2022).Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes**.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,61.

Zhang, Xin,et al."Modulating the Frontier Orbitals of an Aluminylene for Facile Dearomatization of Inert Arenes**".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61(2022).