Green Chemistry
Paper
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Conclusions
We developed an easy and efficient TBPB-promoted P–S coup-
ling reaction for synthesizing thiophosphinates/phosphono-
thioates. The reaction was conducted without the presence of
metallic catalysts at room temperatures (for H-phosphinate
ester 50 °C) and afforded the products in good to excellent
yields. The method also exhibited a great functionality tolerance
for the substrates and a plausible mechanism was proposed.
Experimental
General
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All chemicals were obtained from commercial suppliers or pre-
pared according to the former reference (see ESI†). 1H NMR and
13C NMR spectra were recorded on a Bruker ARX-400. Mass
spectra were performed on a Bruker Esquire 3000 plus mass
spectrometer equipped with ESI interface and ion trap analyzer.
General procedure A: for the preparation of products 3a–3q
(for thiol substrates)
Thiol (0.5 mmol), H-phosphine oxides/H-phosphinate esters
(0.75 mmol) and TBPB (1.0 mmol) were dissolved in 1.5 ml
DMSO in a round-bottom flask, then KI (0.1 mmol) was added
and reacted at room temperature for 4 h. After reaction com-
pletion, the mixture was quenched with 15 ml of Na2S2O4 solu-
tion (5%) and extracted with ethyl acetate (3 × 15 ml). The
combined organic layer was then dried with anhydrous Na2SO4
and evaporated under vacuum. The crude product was purified
by silica gel column chromatography, using PE–EtOAc (3 : 1) as
the eluent.
General procedure B: for the preparation of products 5a–5q
(for thiophenol substrates)
Thiophenol (0.5 mmol), H-phosphine oxides/H-phosphinate
esters (0.75 mmol) and TBPB (0.6 mmol) were dissolved in
1.5 ml DMSO in a round bottomed flask, then KI (0.1 mmol)
was added and reacted at room temperature for 8 h. After
reaction completion, the mixture was quenched with 15 ml
of Na2S2O4 solution (5%) and extracted with ethyl acetate
(3 × 15 ml). The combined organic layer was then dried with
anhydrous Na2SO4 and evaporated in a vacuum. The crude
product was purified by silica gel column chromatography
using PE–EtOAc (3 : 1) as the eluent.
Acknowledgements
The authors gratefully acknowledge financial support from the
National Science Foundation of China (21025207).
Notes and references
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