(R)-2-Methyl-N-(3-(naphthalen-1-yl)allyl)propane-2-sulfinamide
(1f)
1.5 M, 0.125 mmol). After being stirred at 40 °C for 0.5–1 h,
the mixture was concentrated under reduced pressure. The
residue was purified by silica gel column chromatography to
afford the corresponding addition product 3.
1H NMR (300 MHz, CDCl3): δ 1.26 (s, 9H), 3.45 (t, J = 5.4 Hz,
1H), 3.93–4.15 (m, 2H), 6.28 (dt, J = 15.6, 6.3 Hz, 1H), 7.34 (d,
J = 15.3 Hz, 1H), 7.40–7.59 (m, 4H), 7.77 (d, J = 8.1 Hz, 1H),
7.84 (d, J = 8.7 Hz, 1H), 8.09 (d, J = 7.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3): δ 22.78, 48.17, 55.94, 123.76, 124.08,
125.66, 125.91, 126.25, 128.24, 128.62, 129.81, 129.83, 131.16,
133.65, 134.30; IR (KBr): v 3450, 3360, 3218, 2919, 1625,
1429, 1343, 1061, 942, 863, 732 cm−1; ESI-MS: 288.0
[M + H]+, 575.0 [2M + H]+; HRMS (ESI) for C17H21NOSNa
[M + Na]+: calcd 310.1242, found 310.1224.
Acknowledgements
Financial support from the National Natural Science Foundation
of China (20972172, 21021063), the Chinese Academy of
Sciences, SIMM and National Science & Technology Major
Project is greatly acknowledged.
Notes and References
(R)-2-Methyl-N-(3-(naphthalen-2-yl)allyl)propane-2-sulfinamide
1 (a) New Frontiers in Asymmetric Catalysis, ed., K. Mikami and
M. Lautens, Wiley, New Jersey, 2007; (b) Catalysis in Asymmetric Syn-
thesis, 2nd, ed., V. Caprio and J. M. J. Williams, Wiley, 2009;
(c) Catalytic Asymmetric Synthesis, 3rd, Ed., I. Ojima, Wiley, New
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E. N. Jacobsen, A. Pfaltz and H. Yamamoto, Springer, 2010.
2 (a) Privileged Chiral Ligands and Catalysts, Ed., Q.-L. Zhou, Wiley-
VCH, Weinheim, 2011; (b) Chiral Auxiliaries and Ligands in Asymmetric
Synthesis, J. Seyden-Penne, Wiley-Interscience, 1995.
3 (a) P-Stereogenic Ligands in Enantioselective Catalysis, A. Grabulosa,
Royal Society of Chemistry, Cambridge, U.K., 2011; (b) Phosphorus
Ligands in Asymmetric Catalysis, Ed., A. Börner, Wiley-VCH, Wein-
heim, 2008.
4 (a) Organosulfur Chemistry in Asymmetric Synthesis, ed., T. Toru and
C. Bolm, Wiley-VCH, Weinheim, Germany, 2008; (b) Chiral Sulphur
Ligands: Asymmetric Catalysis, Ed., H. Pellissier, Royal Society of
Chemistry, Cambridge, U.K., 2009; (c) M. Mellah, A. Voituriez and
E. Schulz, Chem. Rev., 2007, 107, 5133; (d) H. Pellissier, Tetrahedron,
2007, 63, 1297.
(1g)
1H NMR (300 MHz, CDCl3): δ 1.26 (s, 9H), 3.37 (s, 1H),
3.90–4.05 (m, 2H), 6.38 (dt, J = 15.6, 6.6 Hz, 1H), 6.74 (d, J =
15.6 Hz, 1H), 7.44–7.46 (m, 2H), 7.59 (d, J = 8.4 Hz, 1H),
7.73–7.84 (m, 4H); 13C NMR (100 MHz, CDCl3): δ 22.80,
48.18, 55.99, 123.63, 126.11, 126.44, 126.64, 126.96, 127.78,
128.11, 128.38, 132.80, 133.17, 133.64, 134.00; IR (KBr): v
3453, 3359, 3226, 3057, 1628, 1411, 1363, 1041, 962, 809,
744 cm−1; ESI-MS: 287.9 [M + H]+, 575.0 [2M + H]+; HRMS
(ESI) for C17H22NOS [M + H]+: calcd 288.1422, found
288.1409.
(R)-N-(3-Cyclohexylallyl)-2-methylpropane-2-sulfinamide (1h)
1H NMR (300 MHz, CDCl3): δ 0.99–1.28 (m, 6H), 1.22 (s, 9H),
1.62–1.72 (m, 4H), 1.91–2.00 (m, 2H), 3.18 (t, J = 5.4 Hz, 1H),
3.58–3.78 (m, 2H), 5.45 (dt, J = 15.3, 6.3 Hz, 1H), 5.61 (dd, J =
15.3, 6.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ 22.72,
26.04, 26.18, 32.80, 32.81, 40.41, 47.99, 55.69, 124.27, 140.17;
IR (KBr): v 3208, 2923, 2850, 1475, 1448, 1363, 1180, 1056,
970, 601 cm−1; ESI-MS: 244.1 [M + H]+, 487.1 [2M + H]+;
HRMS (ESI) for C13H26NOS [M + H]+: calcd 244.1735, found
244.1722.
5 (a) S.-S. Jin, H. Wang and M.-H. Xu, Chem. Commun., 2011, 47, 7230;
(b) W.-Y. Qi, T.-S. Zhu and M.-H. Xu, Org. Lett., 2011, 13, 3410.
6 T. Thaler, L.-N. Guo, A. K. Steib, M. Raducan, K. Karaghiosoff,
P. Mayer and P. Knochel, Org. Lett., 2011, 13, 3182.
7 (a) X. Feng, Y. Wang, B. Wei, J. Yang and H. Du, Org. Lett., 2011, 13,
3300; (b) X. Feng, B. Wei, J. Yang and H. Du, Org. Biomol. Chem.,
2011, 9, 5927; (c) Y. Wang, X. Feng and H. Du, Org. Lett., 2011, 13,
4954.
8 (a) G. Chen, J. Gui, L. Li and J. Liao, Angew. Chem., Int. Ed., 2011, 50,
7681; (b) F. Xue, X. Li and B. Wan, J. Org. Chem., 2011, 76, 7256.
9 For reviews on related chiral diene ligands in asymmetric catalysis, see:
(a) F. Glorius, Angew. Chem., Int. Ed., 2004, 43, 3364; (b) C. Defieber,
H. Grützmacher and E. M. Carreira, Angew. Chem., Int. Ed., 2008, 47,
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(d) C.-G. Feng, M.-H. Xu and G.-Q. Lin, Synlett, 2011, 1345.
10 For our recent work involving chiral diene ligands in asymmetric cataly-
sis: (a) Z.-Q. Wang, C.-G. Feng, M.-H. Xu and G.-Q. Lin, J. Am. Chem.
Soc., 2007, 129, 5336; (b) C.-G. Feng, Z.-Q. Wang, P. Tian, M.-H. Xu
and G.-Q. Lin, Chem.–Asian J., 2008, 3, 1511; (c) C.-G. Feng, Z.-
Q. Wang, C. Shao, M.-H. Xu and G.-Q. Lin, Org. Lett., 2008, 10, 4101;
(d) Z.-Q. Wang, C.-G. Feng, S.-S. Zhang, M.-H. Xu and G.-Q. Lin,
Angew. Chem., Int. Ed., 2010, 49, 5780; (e) L. Wang, Z.-Q. Wang,
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11 Part of this 1,4-addition work was presented at the 7th Sino-US Chem-
istry Professors Conference by an invited speech on June. 28, 2011 in
Guiyang, China. For a very recent progress on using simple chiral sulfina-
mide-based olefin ligand in asymmetric 1,2-addition, see: T.-S. Zhu,
S.-S. Jin and M.-H. Xu, Angew. Chem., Int. Ed., 2011, DOI: 10.1002/
anie.201106972.
(R)-N-(3,3-Diphenylallyl)-2-methylpropane-2-sulfinamide (1i)
1H NMR (300 MHz, CDCl3): δ 1.21 (s, 9H), 3.42 (t, J = 4.5 Hz,
1H), 3.73–3.92 (m, 2H), 6.14 (t, J = 6.6 Hz, 1H), 7.16–7.39 (m,
10H); 13C NMR (100 MHz, CDCl3): δ 22.65, 44.93, 55.79,
125.63, 127.52, 127.60, 128.18, 128.36, 129.67, 138.89, 141.66,
144.41; IR (KBr): v 3500, 3342, 3147, 2923, 1597, 1444, 1363,
1143, 1049, 756, 700 cm−1; ESI-MS: 314.0 [M + H]+, 627.0
[2M + H]+; HRMS (ESI) for C19H24NOS [M + H]+: calcd
314.1579, found 314.1564.
General procedures for Rh-Catalyzed 1,4-additions
Under a N2 atmosphere, a solution of [RhCl(C2H4)2]2 (1.5 mg,
0.00375 mmol of Rh), 1b (1.8 mg, 0.0075 mmol), and arylboro-
nic acid (0.60 mmol) in 0.5 mL of dioxane was stirred at 40 °C
for 30 min. To this mixture were added the α,β-unsaturated car-
bonyl compounds (0.25 mmol) and then aqueous K3PO4 (83 μL,
12 (a) T. Hayashi, M. Takahashi, Y. Takaya and M. Ogasawara, J. Am.
Chem. Soc., 2002, 124, 5052; (b) T. Hayashi, K. Ueyama, N. Tokunaga
and K. Yoshida, J. Am. Chem. Soc., 2003, 125, 11508; (c) K. Fagnou and
M. Lautens, Chem. Rev., 2003, 103, 169; (d) T. Hayashi and
K. Yamasaki, Chem. Rev., 2003, 103, 2829.
1768 | Org. Biomol. Chem., 2012, 10, 1764–1768
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