Synthesis of Disubstituted Phosphinates via Palladium-Catalyzed Hydrophosphinylation
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Procedure for Hydrophosphinylation with Phenyl-H-
phosphinic Acid (Table 1)
To
a solution of phenyl-H-phosphinic acid (2 mmol),
Pd2dba3 (5 mol%) and nixantphos polymer (5.5 mol%,
0.35 mmolgÀ1 of nixantphos) in freshly distilled toluene was
added 1-octene (2 mmol) at room temperature under nitro-
gen. The reaction mixture was then heated at reflux for 24 h
under N2. After cooling down, the reaction mixture was fil-
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tered through a fritted funnel and concentrated un vacuum
to afford the product (>94% purity when the
31
P NMR
yield of the crude reaction mixture was ~100%, entries 5–6).
For reactions where the 31 P NMR yield was not quantitative
(entries 1–4), an extractive work-up was conducted. The
crude oil was dissolved in EtOAc and washed with brine
(2ꢄ). The organic layer was dried over MgSO4 and concen-
trated under vacuum to afford the product.
General Procedure for Table 2
To a round-bottom flask equipped with a condenser were
added successively H-phosphinic acid (2 mmol), Pd2dba3
(18 mg, 0.004 mmol, 0.01 equiv., 2 mol% Pd), xantphos
(24 mg, 0.042 mmol, 0.021 equiv.) and ethylene glycol
(10 mL). 1-Octene (0.31 mL, 2 mmol, 1 equiv) was added
via syringe to the purple suspension. After addition, the
mixture was flushed with N2 for 10 min, then heated at
1108C for 24 h, under N2. After cooling to room tempera-
ture, the red-brown solution was extracted with toluene
(3ꢄ). The toluene layers were combined and concentrated
under vacuum. The resulting oil was taken up in Et2O and
treated with aqueous NaOH (1M) in order to remove un-
reacted H-phosphinates. The aqueous layer was again ex-
tracted with Et2O (2ꢄ). The organic layers were combined,
washed with brine, dried over MgSO4 and concentrated to
afford the corresponding product.
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Acknowledgements
We gratefully acknowledge the National Science Foundation
(CHE-0953368) for financial support
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