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Chain Extension of Boronic Esters with Lithiooxiranes
Org. Biomol. Chem. 2006, 4, 2193–2207; b) J. L. Stymiest, G.
fer to the number of attached hydrogen atoms as revealed by the
DEPT spectral editing technique. Low- (MS) and high-resolution
mass spectra (HRMS) were obtained by using either the electron
impact (EI) or electrospray (ES) ionization techniques. Ion mass/
charge (m/z) ratios are reported in atomic mass units.
Dutheuil, A. Mahmood, V. K. Aggarwal, Angew. Chem. Int.
Ed. 2007, 46, 7491–7494; Angew. Chem. 2007, 119, 7635; c) J. L.
Stymiest, V. Bagutski, R. M. French, V. K. Aggarwal, Nature
2008, 456, 778–783; d) V. Bagutski, R. M. French, V. K. Aggar-
wal, Angew. Chem. Int. Ed. 2010, 49, 5142–5145; e) D. J. Blair,
C. J. Fletcher, K. M. P. Wheelhouse, V. K. Aggarwal, Angew.
Chem. Int. Ed. 2014, 53, 5552–5555. Reviews: f) H. K. Scott,
V. K. Aggarwal, Angew. Chem. Int. Ed. 2011, 17, 13124–13132;
g) S. P. Thomas, R. M. French, V. Jheengut, V. K. Aggarwal,
Chem. Rec. 2009, 9, 24–39.
Representative Procedure – (1R,2S)-1,2-Dimethyl-1,4-diphenylbut-
an-1,2-diol (33a): A stirred solution of tBuLi (0.072 mL, 1.52 m in
pentane, 0.109 mmol) in anhydrous THF (1.0 mL) at –100 °C un-
der Ar was treated with a mixture of sulfinyl epoxide 20c (30 mg,
0.105 mmol) and B-phenethyl pinacol boronate (1, R0 = BnCH2,
19 mg, 0.082 mmol)[1b] in anhydrous THF (1.0 mL). The resulting
mixture was stirred for 20 min at –100 °C, then treated with
TBSOTf (0.020 mL, d = 1.151, 23 mg, 0.087 mmol), warmed to
room temp. over 2 h, and stirred for a further 2 h at room temp.
The mixture was then cooled to 0 °C, treated with aq. NaOH
(1.0 mL, 2.0 m) followed by 30 wt.-% aq. H2O2 (0.50 mL), and
stirred for 2 h at 0 °C. The mixture was partitioned between
CH2Cl2 (5 mL) and H2O (3 mL), and the layers were separated.
The aqueous phase was extracted with CH2Cl2 (3ϫ 5 mL), and the
combined organic phases were washed with brine (5 mL), dried
(Na2SO4), and concentrated in vacuo. The residue was purified by
column chromatography (SiO2, eluting with 30% Et2O in hexanes)
to afford the desired anti-like 3°/3° diol 33a (13 mg, 0.048, 59%) as
[5]
StReCH with lithiated triisopropylbenzoate esters: a) R. La-
rouche-Gauthier, C. J. Fletcher, I. Couto, V. K. Aggarwal,
Chem. Commun. 2011, 47, 12592–12594; b) A. P. Pulis, D. J.
Blair, E. Torres, V. K. Aggarwal, J. Am. Chem. Soc. 2013, 135,
16054–16057.
StReCH with lithiated epoxides: E. Vedrenne, O. A. Walker, M.
Vitale, F. Schmidt, V. K. Aggarwal, Org. Lett. 2009, 11, 165–
168.
StReCH with lithiated aziridines: F. Schmidt, F. Keller, E. Ved-
renne, V. K. Aggarwal, Angew. Chem. Int. Ed. 2009, 48, 1149–
1152; Angew. Chem. 2009, 121, 1169.
StReCH with lithiated N-Boc-pyrrolidine: I. Coldham, J. J. Pa-
tel, S. Raimbault, D. T. E. Whittaker, H. Adams, G. Y. Fang,
V. K. Aggarwal, Org. Lett. 2008, 10, 141–143.
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and Epoxides in Organic Synthesis (Ed.: A. K. Yudin), Wiley-
VCH, Weinheim, 2006, pp. 145–184. A lithiated epoxide was
recently directly observed and characterized by NMR spec-
troscopy and X-ray diffraction, see: c) A. Salomone, F. M.
Perna, A. Falcicchio, S. O. Nilsson Lill, A. Moliterni, R.
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[6]
[7]
[8]
[9]
a colorless oil. IR (neat): ν = 3440, 3063, 3028, 2983, 2930, 1604,
˜
1
1496, 1447, 1375, 1058, 1029, 760, 702 cm–1. H NMR (400 MHz,
CDCl3): δ = 7.49 (dm, J = 7.3 Hz, 2 H), 7.33 (tm, J = 8.0 Hz, 2
H), 7.29–7.22 (m, 3 H), 7.15 (tm, J = 7.3 Hz, 1 H), 7.10 (dm, J =
7.1 Hz, 2 H), 2.72 (td, J = 13.4, 4.7 Hz, 1 H), 2.54 (td, J = 12.5,
5.2 Hz, 1 H), 2.42 (s, 1 H), 1.97 (s, 1 H), 1.84 (td, J = 13.7, 4.9 Hz,
1 H), 1.68 (s, 3 H), 1.50 (ddd, J = 13.9, 12.3, 5.3 Hz, 1 H), 1.33 (s,
3 H) ppm. 13C NMR (175 MHz, CDCl3): δ = 144.4 (0), 142.8 (0),
128.4 (2 C, 1), 128.3 (2 C, 1), 127.8 (2 C, 1), 127.0 (1), 126.7 (2 C,
1), 125.7 (1), 79.2 (0), 38.2 (2), 30.1 (2), 24.8 (3), 21.1 (3) ppm (one
RRЈMeCOH signal obscured by CDCl3) ppm. MS (ES+): m/z =
293 [M + Na]+. HRMS (ES+): calcd. for C18H22NaO2 293.1517;
found 293.1531.
[10]
[11]
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, characterization data, and 1H and
13C NMR spectra for all compounds.
[12]
Sulfoxide–metal exchange is also known as sulfoxide–ligand ex-
change. For relevant seminal work, see: a) J. P. Lockard, C. W.
Schroeck, C. R. Johnson, Synthesis 1973, 485–486; b) T. Durst,
M. J. LeBelle, R. Van den Elzen, K. C. Tin, Can. J. Chem.
1974, 52, 761–766; c) T. Satoh, K. Takano, Tetrahedron 1996,
52, 2349–2358; d) R. W. Hoffmann, P. G. Nell, R. Leo, K.
Harms, Chem. Eur. J. 2000, 6, 3359–3365.
Acknowledgments
Financial support for this work by the National Science Founda-
tion (US) (grant CHE-0906409) is gratefully acknowledged. E. A.
thanks the Libyan–North American Scholarship Program adminis-
tered by the Canadian Bureau for International Education for a
scholarship.
[13]
[14]
P. J. Rayner, P. O’Brien, R. A. J. Horan, J. Am. Chem. Soc.
2013, 135, 8071–8077.
CCDC-1012560 (for 16c), -1012561 (for 18t), -1012563 (for
20c), -1000350 (for 20t), -1012562 (for 31a), and -1012564 (for
32a) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.a-
c.uk/data_request/cif.
a) T. Satoh, H. Momochi, T. Noguchi, Tetrahedron: Asymmetry
2010, 21, 382–384; b) T. Kimura, T. Tsuru, H. Momochi, T.
Satoh, Heteroat. Chem. 2013, 24, 131–137.
For example, synthesis of the cis-epoxide epimer of 16c (epi-
meric at sulfur and therefore of the threo type) by the nucleo-
philic epoxidation method of Fernández de la Pradilla was
found to result in material with Ͼ98% ee from the correspond-
ing enantiopure cis-vinyl sulfoxide precursor, see: R.
Fernández de al Pradilla, S. Castro, P. Manzano, M. Martin-
Ortega, J. Priego, A. Viso, A. Rodríguez, I. Fonseca, J. Org.
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[1] For an introduction to stereospecific reagent-controlled homol-
ogation (StReCH) and its mechanistic requirements, see: a)
P. R. Blakemore, S. P. Marsden, H. W. Vater, Org. Lett. 2006,
8, 773–776; b) P. R. Blakemore, M. S. Burge, J. Am. Chem. Soc.
2007, 129, 3068–3069.
[2] a) V. Capriati in Contemporary Carbene Chemistry (Eds.: R. A.
Moss, M. P. Doyle), Wiley, New York, 2014, pp. 327–362; b)
V. Capriati, S. Florio, Chem. Eur. J. 2010, 16, 4152–4162.
[3] StReCH with α-chloroalkyllithiums, see ref.[1] and: a) C. R.
Emerson, L. N. Zakharov, P. R. Blakemore, Org. Lett. 2011,
13, 1318–1321; b) X. Sun, P. R. Blakemore, Org. Lett. 2013,
15, 4500–4503; c) C. R. Emerson, L. N. Zakharov, P. R. Blake-
more, Chem. Eur. J. 2013, 19, 16342–16356.
[15]
[16]
[17]
[4] Selected examples of StReCH with lithiated carbamates: a) G.
Besong, K. Jarowicki, P. J. Kocienski, E. Sliwinski, F. T. Boyle,
a) A. Miyasaka, T. Amaya, T. Hirao, Chem. Eur. J. 2014, 20,
1615–1621; b) R. A. Batey, A. N. Thadani, D. V. Smil, A. J.
Eur. J. Org. Chem. 0000, 0–0
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