Cross‐Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate‐Determining Deprotonation of Bound Hydrazine

Wang, Justin Y.; Choi, Kyoungmin; Zuend, Stephan J.; Borate, Kailaskumar; Shinde, Harish; Goetz, Roland; Hartwig, John F.

doi:10.1002/anie.202011161

Cross‐Coupling between Hydrazine and Aryl Halides with Hydroxide Base at Low Loadings of Palladium by Rate‐Determining Deprotonation of Bound Hydrazine

Journal Article · Tue Oct 27 00:00:00 EDT 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202011161· OSTI ID:1786208

Wang, Justin Y. ^[1]; Choi, Kyoungmin ^[1]; Zuend, Stephan J. ^[2]; Borate, Kailaskumar ^[3]; Shinde, Harish ^[3]; Goetz, Roland ^[4]; ^[1]

Department of Chemistry University of California Berkeley California 94720 USA
BASF Corp. 46820 Fremont Boulevard Fremont California 94538 USA
Innovation Campus Mumbai, Room No. 6.23 BASF Chemicals India Pvt. Ltd., Plot No. 12, TTC Area Thane Belapur Road, Turbhe Navi Mumbai 400705 India
BASF SE Carl-Bosch-Strasse 38 67056 Ludwigshafen am Rhein Germany

Abstract

Reported here is the Pd‐catalyzed C–N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride. These compounds are present in two interconnected catalytic cycles and react with hydrazine and base or hydrazine alone to give the product. The selectivity of the hydroxide complex with hydrazine to form aryl over diaryl hydrazine was lower than that of the chloride complex, as well as the catalytic reaction. In contrast, the selectivity of the chloride complex closely matched that of the catalytic reaction, indicating that the aryl hydrazine is derived from this complex. Kinetic studies showed that the coupling process occurs by rate‐limiting deprotonation of a hydrazine‐bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1786208

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 1 Vol. 60; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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