Synlett 2015; 26(17): 2403-2407
DOI: 10.1055/s-0034-1378833
cluster
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Cross-Coupling Reaction of Lithiated Monocarba-closo-dodecaborate at the Carbon Vertex

Yu Kitazawa
a  Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: uchiyama@mol.f.u-tokyo.ac.jp
b  RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan   Email: ryo.takita@riken.jp
,
Mai Otsuka
a  Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: uchiyama@mol.f.u-tokyo.ac.jp
,
Junichiro Kanazawa
a  Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: uchiyama@mol.f.u-tokyo.ac.jp
,
Ryo Takita*
b  RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan   Email: ryo.takita@riken.jp
,
Masanobu Uchiyama*
a  Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan   Email: uchiyama@mol.f.u-tokyo.ac.jp
b  RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan   Email: ryo.takita@riken.jp
› Author Affiliations
Further Information

Publication History

Received: 08 April 2015

Accepted after revision: 11 May 2015

Publication Date:
19 June 2015 (online)


Dedicated to Professor Manfred Schlosser for his outstanding contribution in organic and organometallic chemistry.

Abstract

A cross-coupling reaction of lithium species of monocarba-closo-dodecaborate {[closo-CHB11H11]} at the carbon vertex under palladium catalysis was developed. The properties of a metal–carborate complex in a transmetalation step were important to achieve the cross-coupling process with aryl halides, and the use of lithiated monocarba-closo-dodecaborate was found to promote the carbon–carbon bond formation to provide a series of C-arylated monocarba-closo-dodecaborate derivatives. Mechanistic investigations with DFT calculations suggested the efficient transmetalation with the lithium reagent.

Supporting Information

 
  • References and Notes

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  • 9 A substantial amount of iodinated 1 was observed by ESI-MS analysis, while the quantification was not done due to the overlap of peaks with unreacted 1 in 11B NMR or 1H NMR spectra.
  • 10 A ketone-type byproduct generated by the nucleophilic addition of 1a to the carbonyl group of 2g was obtained in ca. 30% yield.
  • 11 Some aryl iodides having strong electron-withdrawing substituents, such as cyano group, caused the undesired halogen–lithium exchange reaction with the poor C–C bond formation. For these substrates, the previous conditions5a should be utilized.
  • 12 The calculations were performed at the B3LYP/SDD (for Pd, I) and 6-31+G* (for other atoms) level of the theory. All calculations were carried with the Frisch, M. J. et al. Gaussian 09, Revision C.01; Gaussian, Inc., Wallingford, CT, 2009. The full citation is given in the Supporting Information.
  • 13 While the precise mechanism of trans- to cis-isomerization has not been clarified, we speculate that another arylpalladium complex should be involved via the second transmetalation. The low energy difference (>1 kcal/mol) between two isomers has been found by DFT calculations (see Supporting Information).
  • 14 With the boron–carborate complex, the transmetalation rection to give cis-Pd(Ph)(carborate)(PMe3) is found to need ca. 40 kcal/mol, in accordance with the experimental results. Detailed results will be separately reported in due course.