Zinc-Mediated Stereoselective Barbier Allylation of N-Carbethoxy-α-amino Ketones in Aqueous Solution

Gabriel O. Resende; Lucia C. S. Aguiar; O. A. C. Antunes

doi:10.1055/s-2004-836039

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Synlett 2005(1): 119-120
DOI: 10.1055/s-2004-836039

LETTER

Zinc-Mediated Stereoselective Barbier Allylation of N-Carbethoxy-α-amino Ketones in Aqueous Solution

Gabriel O. Resende^a, Lucia C. S. Aguiar*^a, O. A. C. Antunes^b
^a Núcleo de Pesquisas de Produtos Naturais, UFRJ, Cidade Universitária, CCS Bloco H, Rio de Janeiro, RJ 21941-590, Brazil
e-Mail: lcsequeira@nppn.ufrj.br;
^b Instituto de Química, UFRJ, Cidade Universitária, CT Bloco A, Lab 641, Rio de Janeiro, RJ 21941-590, Brazil

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Publication History

Received 3 September 2004
Publication Date:
29 November 2004 (online)

Abstract
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Abstract

Zinc-mediated aqueous allylic Barbier reaction of N-carbethoxy-α-amino phenylketones was carried out with good diastereoselectivity (up to 95% de), leading to vicinal amino alcohols. The corresponding reaction using N-carbethoxy-α-amino methylketones did not present good facial diastereoselectivity.

Key words

diastereoselectivity - zinc - allylations - amino ketones - Barbier reaction

References

1 Li C.-J. Tetrahedron 1996, 52: 5643

Crossref Search in Google Scholar
2a Hanessian S. Park H. Yang R.-Y. Synlett 1997, 353

Crossref
2b Hanessian S. Park H. Yang R.-Y. Synlett 1997, 351

Crossref
2c Jurczak J. Krasinski A. Tetrahedron Lett. 2001, 42: 2019

Crossref Search in Google Scholar
2d Giannis A. Seck S. Rubsam F. Tetrahedron 1997, 53: 2823

Crossref Search in Google Scholar
3a Kabalka GW. Pace RD. J. Org. Chem. 1995, 60: 4838 ; and references therein

Crossref Search in Google Scholar
3b Loh T.-P. Huang J.-M. Xu K.-C. Go S.-H. Vittal JJ. Tetrahedron Lett. 2000, 41: 6511

Crossref Search in Google Scholar
4 Rapoport H. Buckley TF. J. Am. Chem. Soc. 1981, 103: 6157

Crossref Search in Google Scholar
5 Gordon EM. Godfrey JD. Von Langen DJ. Tetrahedron Lett. 1987, 28: 1603

Crossref Search in Google Scholar
6 Rich DH. Bernatowicz MS. Boparai AS. Kawai M. J. Org. Chem. 1983, 48: 1876

Search in Google Scholar
7 Mullen G. Napier J. Balestra M. DeCory T. Hale G. Macor J. Mack R. Loch J. Wu E. Kover A. Verhoest P. Sampognaro A. Phillips E. Zhu Y. Murray R. Griffith R. Blosser J. Gurley D. Machulskis A. Zongrone J. Rosen A. Gordon J. J. Med. Chem. 2000, 43: 4045

Crossref Search in Google Scholar
8a Azzolina O. Collina S. Brusotti G. Rossi D. Linati L. Lanza E. Ghislandi V. Tetrahedron Lett. 2004, 45: 1355

Search in Google Scholar
8b Collina S. Azzolina O. Vercesi D. Benevelli F. Callegari A. Tadini C. Lanza E. Barbieri A. Ghislandi V. Bioorg. Med. Chem. 2000, 8: 769

Search in Google Scholar
9 Yao Z.-J. Zha H.-Y. Qin D.-G. J. Org. Chem. 2002, 67: 1038

Crossref Search in Google Scholar
10 Liotta DC. Crane HM. Lagu BR. J. Org. Chem. 1993, 58: 4191

Search in Google Scholar

11

General Procedure for the Allylation of Amino Ketones 2a-f:
Zinc dust (6 mmol) was added to a solution of the N-protected α-amino ketones (1 mmol) and allyl bromide (3 mmol) in sat. aq NH₄Cl-THF (5 mL:1 mL) at 0 °C (ca. 1 h). Filtration, extraction (EtOAc), and evaporation gave the desired products after column chromatography (10-15% EtOAc in hexane).

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Analytical data for amino alcohols obtained:
Compound 1a: [α]_D +45.8 (c 0.9, CH₂Cl₂). ¹H NMR (200 MHz, CDCl₃): δ = 7.40-7.20 (m, 5 H), 5.50-5.28 (m, 1 H), 5.20-5.02 (m, 3 H), 4.16 (q, J = 6.96 Hz, 2 H), 4.16-3.94 (m, 1 H), 2.81 (dd, J = 13.92 and 5.43 Hz, 1 H), 2.62 (dd, J = 13.55 and 8.79 Hz, 1 H), 1.27 (t, J = 7.14, 3 H), 0.87 (d, J = 6.59, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.50, 16.03, 44.10, 54.01, 60.75, 77.71, 119.92, 125.29, 126.69, 128.10, 132.94, 143.33, 156.57.
Compound 1b: [α]_D +7.5 (c 2, CH₂Cl₂). ¹H NMR (200 MHz, CDCl₃): δ = 5.46-5.22 (m, 1 H), 5.20-5.02 (m, 2 H), 4.84 (br d, 1 H), 4.17 (q, J = 7.08 Hz, 2 H), 4.12-3.80 (m, 1 H), 2.80 (dd, J = 13.67 and 4.96 Hz, 1 H), 2.57 (dd, J = 13.73 and 9.09 Hz, 1 H), 1.62-1.42 (m, 2 H), 1.28 (t, J = 7.14, 3 H), 1.32-1.22 (m, 1 H), 0.76 (d, J = 6.72, 3 H), 0.75 (d, J = 6.47, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.53, 21.01, 23.68, 24.51, 38.84, 44.39, 56.58, 60.83, 78.36, 119.97, 125.29, 126.64, 128.14, 132.97, 143.58, 157.16.
Compound 1c: [α]_D +25.2 (c 1,5, CH₂Cl₂). ¹H NMR (200 MHz, CDCl₃): δ = 7.64-6.80 (m, 10 H), 5.50-5.20 (m, 1 H), 5.20-5.00 (m, 3 H), 4.26 (td, J = 9.46 and 5.37 Hz, 1 H), 4.00 (q, J = 7.08 Hz, 2 H), 2.85 (dd, J = 13.92 and 8.79 Hz, 1 H), 2.64 (dd, J = 13.92 and 9.04 Hz, 1 H), 2.54-2.46 (m, 2 H), 1.12 (t, J = 7.08 Hz, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.43, 35.90, 44.51, 59.95, 60.70, 78.20, 119.91, 125.30, 125.89, 126.84, 127.98, 128.31, 128.85, 132.90, 138.61, 143.55, 156.81.
Compound 1d: ¹H NMR (200 MHz, CDCl₃): δ = 6.00-5.75 (m, 1 H), 5.20-5.05 (m, 3 H), 4.11 (q, J = 7.11 Hz, 2 H), 3.75-3.55 (m, 1 H), 2.27 (d, J = 7.44 Hz, 2 H), 1.24 (t, J = 7.08 Hz, 3 H), 1.17 (d, J = 6.82 Hz, 3 H), 1.13 (s, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.41, 15.54 (15.76), 22.97 (24.00), 43.39 (44.02), 53.15 (53.61), 60.73, 73.84 (73.95), 118.64, 133.36, 156.58 (156.73).
Compound 1e: ¹H NMR (200 MHz, CDCl₃): δ = 6.00-5.80 (m, 1 H), 5.20-5.05 (m, 2 H), 4.70 (br d, 1 H), 4.10 (q, J = 6.90 Hz), 3.72-3.50 (m, 1 H), 2.40-2.08 (m, 2 H), 1.65-1.58 (m, 2 H), 1.41-1.30 (m, 1 H), 1.24 (t, J = 7.14 Hz, 3 H), 0.93 (d, J = 6.59 Hz, 3 H), 0.90 (d, J = 6.32 Hz, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.33, 21.18, 22.81, 23.82, 24.69, 38.36 (38.68), 43.39 (44.00), 55.98 (56.17), 60.65 (60.74), 74.33 (74.49), 118.36, 133.46, 157.10 (157.34). Compound 1f: ¹H NMR (200 MHz, CDCl₃): δ = 7.32-7.12 (m, 5 H), 6.06-5.80 (m, 1 H), 5.26-5.08 (m, 2 H), 4.84 (m, 1 H), 3.94 (q, J = 6.96 Hz, 2 H), 3.86-3.64 (m, 1 H), 3.20-2.98 (m, 1 H), 2.70-2.22 (m, 3 H), 1.25 (s, 3 H), 1.10 (t, J = 7.13, 3 H). ¹³C NMR (50 MHz, CDCl₃): δ = 14.35, 23.62 (24.27), 35.39 (35.64), 43.92 (44.37), 59.30 (59.41), 60.75, 74.16 (74.28), 118.76 (118.95), 126.08, 128.17, 128.97, 138.50 (138.64), 156.80 (157.05).