10.1002/adsc.201901303
Advanced Synthesis & Catalysis
To a 50 mL dried Schlenk tube equipped with a magnetic
stir bar were added p-quinone monoacetal 2 (10 mmol,
1.542 g) and CH3CN (2 mL) under N2. After the mixture
was stirred at 0 oC for 30 min, a solution of PMe3 (1.0 M in
toluene, 11 mmol, 11 mL) was added dropwise. The
reaction mixture was slowly warmed to room temperature
and stirred overnight. The product precipitated out as white
solid. After centrifugation and filtration of the reaction
mixture, the white solid product was collected. The
obtained solid was washed by a small portion of toluene
and CH3CN, and was dried under high vacuum to give the
pure product 1 in 92% yield (1.820 g). white solid, mp.
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1
208.5oC-209.7oC. H NMR (400 MHz, CD3CN): δ 6.77 (t,
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J = 8.8 Hz, 1H), 6.41 (dd, J1 = 9.2 Hz, J2 = 2.8 Hz, 1H),
6.17 (dd, J1 = 17.2 Hz, J2 = 2.8 Hz, 1H), 3.74 (s, 3H), 1.94
(d, J = 14.4 Hz, 9H). 13C NMR (100 MHz, D2O): δ 160.64
(d, J = 14.5 Hz), 151.33, 126.00 (d, J = 2.7 Hz), 119.79 (d,
J = 7.0 Hz), 114.45 (d, J = 9.0 Hz), 108.31 (d, J = 87.2 Hz),
56.39, 8.85 (d, J = 57.9 Hz). 31P NMR (162 MHz,
CD3CN): δ 16.66. Elemental analysis calculated (%) for (1
·½ H2O): C, 57.96; H, 7.78. Found: C, 57.64; H, 7.81.
Note: since compound 1 is hydroscopic, water in air might
contaminate the sample to give this result during the
elemental analysis experiment.
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General procedures for 1-catalyzed H/D exchange
reactions
A mixture of the substrate (0.1 mmol or 0.2 mmol) and 5
mmol% 1 in 0.4 mL CD3CN was charged in a heavy-
walled NMR tube fitted with a re-sealable Teflon valve (J
Young tube) in the glovebox under N2. Then the mixture
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7513–7515; c) A. P.-Davtyan, R. Jackstell, A.
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Y. Huang, Tetrahedron Lett., 2019, 60, 1015–1018; e)
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o
was heated at 80 C for indicated time. After the mixture
was cooled to room temperature, the crude mixture was
1
analyzed by H NMR to determine the deuteration of the
product.
Typical procedure for olefination of aldehydes with 1
or 1-d9 and characterization data of the products
A
mixture of an aldehyde (0.1 mmol) and the
phosphonium zwitterion 1 (0.1 mmol, 19.8 mg) in dioxane
(1.0 mL) was stirred at 120 oC for indicated time. After the
mixture was cooled to room temperature, the mixture was
passed through a short silica gel column with EtOAc as
eluent. The filtrate was concentrated and the residue was
further purified by column chromatography on silica gel to
give the product 6.
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4760–4768.
Acknowledgements
JX thanks a postdoc fellowship from AIST and partial support
from National Natural Science Foundation of China (21703061).
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