10.1002/chem.202001517
Chemistry - A European Journal
solvents were dried using a solvent purification system (SPS). EDA,
Acknowledgements
NaBArF , reagents and substrates were purchased from Sigma-
4
The authors would like to thank the financial support of the
MINECO (CTQ2017-82893-C2-1-R), and PO FEDER 2014–2020,
(UHU-1260216).
Aldrich
and
used
without
previous
purification.
The
bromodiaminophosphine 1,[8] PhEDA[24] and MEDA[25] were prepared
according to literature methods. Elemental analyses were performed
on a PerkinElmer Series II CHNS/O Analyzer 2400. High Resolution
Mass Spectroscopy (HRMS) experiments were carried out at the
Centre of Research Technology and Innovation of the University of
Seville (CITIUS). Enantiomeric excess was measured with a HPLC
Waters 1525. X-Ray diffraction studies were performed in a BRUKER
D8 FIXED-CHI diffractometer equipped with an Oxford Cryosystem
low-temperature device.
Conflict of interest
The authors declare no conflict of interest.
Keywords: alkoxydiaminophosphine ligands • copper phosphine
complexes • C-H activation • carbene and nitrene transfer •
CuAAC
Generation of alkoxydiamidophosphine ligands (ADAPs).
Under N2 atmosphere, the alcohol (1 mmol) and Et3N (1.2 mmol)
were added to a solution of 1,3-bis[2,6-bis(1-methylethyl)phenyl]-2-
bromo-2,3-dihydro-1H-1,3,2-diazaphospholene (1) (1 mmol) in
toluene (5 mL). The reaction mixture was stirred for 12 h at room
temperature and after this time the ammonium salt precipitates as a
white solid. The reaction is heated at 110 ºC for 1 extra hour and the
mixture cooled to room temperature. The solid was filtered and the
solution was checked by 31P{1H} showing the formation of ADAP
ligands 2a-f. In the case of 2b/2c, removal of volatiles gave a solid
which could be characterized by 31P{1H} NMR using concentrated
samples and employing a few minutes of acquisition.
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Synthesis of the copper complexes (ADAP)CuCl (3a-f).
The in situ generated toluene solutions of ADAP ligands (2a-2f)
were transferred via cannula into flame-dried Schlenk flask containing
CuX (X = Cl, Br; 1mmol). After 4 hours, the mixture was filtered, and
the filtrate was evaporated under reduced pressure. The solid residue
was washed with hexane (2 x 20 mL) to afford the desired products
3a-3f and 3a-Br as off-white solids with analytical purity. Single
crystals of 3a-Br were grown from acetone solutions at -30 ºC. See SI
for full characterization data. Crystallographic data has been
deposited at CCDC with code number 1993132.
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Carbene transfer reactions.
The catalyst (0.0125 mmol), NaBArF (0.0125 mmol) and the
4
olefin (0.7 mmol) were dissolved in DCM (4 mL). The diazocompound
(0.5 mmol) was added portionwise (one portion of 12 l every 30 min
for 7 hours). The resulting mixture was stirred at room temperature for
additional 12 h before reaction analysis. The experiments with amines,
alkanes and benzene were carried out following a similar same
procedure. See SI for details.
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Copper-catalyzed Azide Alkyne Cycloaddition.
The copper complex (3a, 0.0125 mmol), NaBArF4 (0.0125 mmol),
the azide (0.125 mL) and phenylacetylene (0.11 mL) were dissolved
in 4 mL of DCM. The resulting mixture was stirred at room
temperature for 4 h. After this time, volatiles were removed under
reduced pressure, and the residue investigated by NMR showing the
exclusive formation of the expected triazole. See SI for details.
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Reaction of 1-phenyl-1-propyne and PhI=NTs.
The copper complex (3a, 0.0125 mmol), NaBArF4 (0.0125 mmol),
the alkyne (2 mmol) were dissolved in 5 mL of DCM before PhI=NTs
(0.2 mmol) was added. The resulting mixture was stirred at room
temperature for 30 minutes. After this time, volatiles were removed
and the residue investigate by NMR. See SI for details.
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