Regioselective B2-6 penta-iodination of the [CB11H12]- monocarborane cluster by palladium catalysis

被引：0

作者：

Lin, Chuhao ^{[1
]}

Jin, Yujie ^{[1
]}

Sun, Jizeng ^{[1
]}

Ye, Zehua ^{[1
]}

Chen, Tao ^{[1
]}

Liu, Jiyong ^{[1
]}

Duttwyler, Simon ^{[1
]}

机构：

[1] Zhejiang Univ, Dept Chem, 866 Yuhangtang Rd, Hangzhou 310058, Peoples R China

来源：

DALTON TRANSACTIONS | 2023年 / 52卷 / 32期

基金：

中国国家自然科学基金;

关键词：

TRANSITION-METAL-COMPLEXES; B-H FUNCTIONALIZATION; SUBSTITUTION SYMMETRY; CARBORANES; ANIONS; BORON; PHARMACOPHORES; ACTIVATION; CHEMISTRY; CL;

D O I：

10.1039/d3dt02275g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Penta-iodination of the B2-6 positions of the {CB11} monocarborane cluster is reported. Products of the structure [2,3,4,5,6-I-5-CB11H6-12-X](-) (X = H, Me, Et, Ph, Br, I) were obtained and fully characterized. X-ray crystal structures of three new compounds confirm this particular substitution pattern. The synthetic method relies on palladium catalysis/B-H activation, assisted by the C1-COOH directing group. The one-pot procedure enables penta-iodination and subsequent decarboxylation under convenient conditions. The B2-6 regioselectivity is complementary to the commonly observed reactivity of {CB11} clusters, which follows the trend B12 > B7-11 > B2-6 for electrophilic substitution. Thus, for the first time upper-belt halogenation is achieved without prior modification of the lower-belt positions.

引用

页码：11042 / 11046

页数：5

共 52 条

[1] B-N bond formation through palladium-catalyzed, microwave-assisted cross-coupling of nitrogen compounds with iodo-dodecaborate
Al-Joumhawy, Mahmoud K.
Marei, Tarek
Shmalko, Akim
Cendoya, Paula
La Borde, Jair
Gabel, Detlef
[J]. CHEMICAL COMMUNICATIONS, 2021, 57 (78) : 10007 - 10010
[2] Thermal and Photophysical Properties of Highly Quadrupolar Liquid-Crystalline Derivatives of the [closo-B12H12]2- Anion
Ali, Muhammad O.
Lasseter, John C.
Zurawinski, Remigiusz
Pietrzak, Anna
Pecyna, Jacek
Wojciechowski, Jakub
Friedli, Andrienne C.
Pociecha, Damian
Kaszynski, Piotr
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2019, 25 (10) : 2616 - 2630
[3] Polyhedral boron clusters in materials science
Dash, Barada Prasanna
Satapathy, Rashmirekha
Maguire, John A.
Hosmane, Narayan S.
[J]. NEW JOURNAL OF CHEMISTRY, 2011, 35 (10) : 1955 - 1972
[4] Synthesis and molecular structure of 12-iodo-1-(4-pentylquinuclidin-1-yl)-1-carba-closo-dodecaborane
Douglass, AG
Janousek, Z
Kaszynski, P
Young, VG
[J]. INORGANIC CHEMISTRY, 1998, 37 (24) : 6361 - 6365
[5] Update 1 of: Chemistry of the Carba-closo-dodecaborate(-) Anion, CB11H12-
Douvris, Christos
Michl, Josef
[J]. CHEMICAL REVIEWS, 2013, 113 (10) : PR179 - PR233
[6] Recent advances in B-H functionalization of icosahedral carboranes and boranes by transition metal catalysis
Duttwyler, Simon
[J]. PURE AND APPLIED CHEMISTRY, 2018, 90 (04) : 733 - 744
[7] Metal-catalyzed cross-coupling chemistry with polyhedral boranes
Dziedzic, Rafal M.
Spokoyny, Alexander M.
[J]. CHEMICAL COMMUNICATIONS, 2019, 55 (04) : 430 - 442
[8] Amphiphiles without Head-and-Tail Design: Nanostructures Based on the Self-Assembly of Anionic Boron Cluster Compounds
Fernandez-Alvarez, Roberto
Dordovic, Vladimir
Uchman, Mariusz
Matejicek, Pavel
[J]. LANGMUIR, 2018, 34 (12) : 3541 - 3554
[9] Nonclassical Applications of closo-Carborane Anions: From Main Group Chemistry and Catalysis to Energy Storage
Fisher, S. P.
Tomich, A. W.
Lovera, S. O.
Kleinsasser, J. F.
Guo, J.
Asay, M. J.
Nelson, H. M.
Lavallo, V.
[J]. CHEMICAL REVIEWS, 2019, 119 (14) : 8262 - 8290
[10] Teaching an old dog new tricks: new directions in fundamental and applied closo-carborane anion chemistry
Fisher, Steven P.
Tomich, Anton W.
Guo, Juchen
Lavallo, Vincent
[J]. CHEMICAL COMMUNICATIONS, 2019, 55 (12) : 1684 - 1701

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