Copper-Catalyzed Germyl-Azidation of Alkenes with Germanium Hydrides and Trimethylsilyl Azide

Abstract

The incorporation of a germyl group and another functional fragment across the CC bond is a challenging task due to the prevailing hydrogermylation reaction. Herein, an efficient copper-catalyzed three-component reaction of alkenes, germanium hydrides, and trimethylsilyl azide has been disclosed. This transformation allows the concomitant introduction of germyl and azide groups across the double bonds in a highly regioselective manner with tert-butyl hydroperoxides as the bystanding oxidant. The resulting β-germyl azides could be easily converted into β-germyl amine and 1,2,3-triazoles of significant value.

Synthesis of 6-membered germacycles by intramolecular germylzincation of alkynes

“…This process was of interest because even though radical hydrogermylation is a well-known and widely developed process, the vast majority of the reports involve intermolecular additions. 22 We thus decided to study the intramolecular hydrogermylation conditions in more detail (conditions B ), and assess its generality with the substrates shown in Scheme 4 (Table 4). Synthetically this was also of interest as conditions B (giving anti -adducts) and conditions A (giving syn -adducts) would thus offer complementary stereodivergent procedures.…”

Carbon–Germanium Bond Formation via Low-Valent Cobalt-Catalyzed Cross-Electrophile Coupling

“…However, the use of organolithium or Grignard reagents may limit the functional group tolerance and wider application. Alternatively, the transition-metal-catalyzed formation of organogermanes has been developed via the coupling of R 3 GeH or its surrogates as germanium sources . In this regard, the Oestreich group has recently reported a Ni-catalyzed Csp 3 –Ge formation coupling of zinc-based germanium nucleophiles with alkyl electrophiles .…”

Access to germasiloxanes and alkynylgermanes mediated by earth-abundant species

“…This strategy has provided an entry point into various organogermanes including germasiloxanes and alkynylgermanes. Remarkably, not only KHMDS but also simple bases such as KOH can serve as efficient catalysts in this process.Organogermanium compounds are much less studied than their silicon counterparts, but very recently, an impetus to design new synthetic routes to various organogermanes was witnessed and significant contributions were reported [1][2][3][4][5][6][7][8][9][10][11] . That is not merely a scientific curiosity but primarily, the unique features of germanium compounds are the leading cause of this trend.…”

“…Organogermanium compounds are much less studied than their silicon counterparts, but very recently, an impetus to design new synthetic routes to various organogermanes was witnessed and significant contributions were reported [1][2][3][4][5][6][7][8][9][10][11] . That is not merely a scientific curiosity but primarily, the unique features of germanium compounds are the leading cause of this trend.…”