2958 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 10
Kieseung Lee and Chan-Yeon Hwang
having alkoxycarbonylphosphorane subunit.
1H, J = 2.9 Hz), 6.94 (dd, 1H, J1 = 4.9 Hz, J2 = 3.4 Hz), 7.14
(dd, 1H, J1 = 4.9 Hz, J2 = 1.0 Hz), 7.45-7.68 (m, 15H); 13
C
NMR (CDCl3, 100 MHz) δ 25.18, 40.48, 40.55, 48.27, 49.52,
122.34, 122.50, 122.68, 123.00, 123.61, 124.53, 126.55,
129.01, 129.13, 132.98, 133.01, 133.49, 133.59, 144.34,
195.00, 195.03; MS (AP/CI) m/z 440 [M+H]+; Anal. calcd
for C27H22NOPS: C, 73.78; H, 5.05; N, 3.19, found: C,
73.60; H, 5.00; N, 3.27.
Acknowledgments. The authors gratefully acknowledge
the financial support from Woosuk University as well as
from the LINC program funded by Korean Ministry of
Education, Science and Technology in 2013.
References and Notes
3-Oxo-6-(tetrahydro-2H-pyran-2-yloxy)-2-(triphenyl-
λ5-phosphanylidene)hexane-nitrile (2'g). The product 2'g
was separated by flash column chromatography on silica gel
(CH2Cl2/EtOAc, 3/1) in 85% yield. An off-white solid; mp
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127-129 C; IR (KBr) 2171, 1595 cm−1; H NMR (CDCl3,
400 MHz) δ 1.45-1.75 (m, 5H), 1.77-1.89 (m, 1H), 1.91-
2.02 (m, 2H), 2.80 (t, 2H, J = 7.6 Hz), 3.38-3.54 (m, 2H),
3.71-3.81 (m, 1H), 3.82-3.93 (m, 1H), 4.61 (t, 1H, J = 3.4
Hz), 7.47-7.67 (m, 15H); 13C NMR (CDCl3, 100 MHz) δ
19.38, 25.45, 25.50, 30.64, 36.10, 36.17, 47.63, 48.89,
61.97, 66.81, 98.50, 122.91, 123.84, 129.00, 129.12, 132.97,
133.00, 133.49, 133.58, 196.64, 196.67; MS (AP/CI) m/z
472 [M+H]+; Anal. calcd for C29H30NO3P: C, 73.87; H,
6.41; N, 2.97, found: C, 73.73; H, 6.45; N, 2.96.
6-(1,3-Dioxan-2-yl)-3-oxo-2-(triphenyl-λ5-phosphanyl-
idene)hexanenitrile (2'h). The product 2'h was separated
by flash column chromatography on silica gel (CH2Cl2/
EtOAc, 2/1) in 80% yield. An off-white solid; mp 142-144
oC; IR (KBr) 2177, 1578 cm−1; 1H NMR (CDCl3, 400 MHz)
δ 1.21-1.37 (m, 1H), 1.55-1.85 (m, 4H), 1.97-2.15 (m, 1H),
2.73 (t, 2H, J = 7.3 Hz), 3.75 (td, 2H, J1 = 12.2 Hz, J2 = 2.4
Hz), 4.09 (dd, 2H, J1 = 10.7 Hz, J2 = 4.9 Hz), 4.55 (t, 1H, J =
4.9 Hz), 7.46-7.69 (m, 15H); 13C NMR (CDCl3, 100 MHz) δ
19.93, 25.89, 34.53, 38.95, 39.02, 47.63, 66.86, 102.18,
122.62, 122.79, 123.00, 123.93, 129.04, 129.16, 132.99,
133.02, 133.56, 133.66, 196.84, 196.88; MS (AP/CI) m/z
458 [M+H]+; Anal. calcd for C28H28NO3P: C, 73.51; H,
6.17; N, 3.06, found: C, 73.62; H, 6.34; N, 3.23.
o
1
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Conclusion
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In summary, we have developed a new synthetic approach
to α-keto (cyanomethylene)triphenylphosphorane ylides
from alkyl halides utilizing a new sulfonyl reagent 8 as the
key reagent. There are several advantages expected from this
new approach, e.g., (i) new sulfonyl reagent 8 is easy to
prepare in good yield, and stable solid to handle at ambient
temperature; (ii) the reaction conditions are mild, and overall
yields are good to excellent; (iii) the reaction procedures are
highly reproducible, and also provide direct access to β,γ-
saturated, α-keto (cyanomethylene)triphenylphosphorane
ylides from alkyl halides. Therefore, this new alkylation-
desulfonylation protocol offers an expeditious approach to
α-keto (cyanomethylene)triphenylphosphorane ylides from
alkyl halides. We are currently trying to apply the same
approach to the synthesis of α-keto alkoxycarbonyltri-
phenylphosphorane ylides,12 triphenylphosphorane ylide
precursors to tricarbonyl units, using a new sulfonyl reagent
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