1,2-Metallate Rearrangements of α-Alkoxyalkyl Cuprates

Krzysztof Jarowicki; Philip J. Kocienski

doi:10.1055/s-2004-836045

LETTER

1,2-Metallate Rearrangements of α-Alkoxyalkyl Cuprates

Krzysztof Jarowicki, Philip J. Kocienski*
School of Chemistry, Leeds University, Leeds LS2 9JT, UK
e-Mail: p.kocienski@chemistry.leeds.ac.uk;

Abstract

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Abstract

α-Alkoxylalkyl cuprates undergo 1,2-metallate rearrangement to give secondary alkyl cuprates.

Key words

1,2-metallate rearrangement - glycosyl cuprates - alkylation - α-alkoxyalkyl cuprates

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Referenzen

References

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<A NAME="RD30904ST-2">2</A> Kocienski PJ. In Organic Synthesis via Organometallics Enders D. Gais H.-J. Keim W. Verlag Vieweg; Wiesbaden: 1993. p.203-223

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We coined the term 1,2-metallate rearrangement to describe a large class of reactions involving nucleophlic displacement reactions of electrophilic carbenoids (see ref. 1).

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<A NAME="RD30904ST-11">11</A> Compounds 14a and 14b were prepared the same way as the corresponding tribenzyl derivatives: Christopher JA. Kocienski PJ. Procter MJ. Synlett 1998, 425

Compounds 17a and 17b were converted into the corresponding methyl ethers 18a and 18b and their structures determined by stereoselective synthesis.

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Selected Spectroscopic Data for Compounds 7, 11, 13, 18a and 18b: Compound 7: IR (neat): 3334, 3076, 2956, 2927, 2860, 1639, 1589, 1456 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 5.78 (1 H, ddt, J = 16.7, 9.8, 7.3 Hz, H₂C=CH), 5.05-4.97 (2 H, m, H ₂C=CH), 3.64 (2 H, q, J = 6.4 Hz, CH ₂OH), 2.10-2.00 (2 H, m, CH ₂CH=CH₂), 1.61-1.53 (2 H, m, C2H₂), 1.46-1.38 (1 H, m, C4H), 1.35-1.21 (9 H, m, OH, 4 × CH₂), 0.90 (3 H, t, J = 6.8 Hz, CH₃). ¹³C NMR (75 MHz, CDCl₃): δ = 137.5 (H₂C=CH), 115.9 (H₂ C=CH), 63.5 (C1H₂), 38.2 (CH₂CH=CH₂), 37.3 (C4H), 33.1 (CH₂CH₂CH₂CH₃), 30.1 (C2H₂), 29.4 (C3H₂), 29.0 (CH₂CH₂CH₃), 23.2 (CH₂CH₃), 14.3 (CH₃). HRMS (ES): m/z calcd for C₁₁H₂₃O [M + H]⁺: 171.1749. Found: 171.1751.
Compound 11: IR (neat): 3336, 3076, 2927, 2859, 1640, 1458 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 5.77 (1 H, ddt, J = 17.1, 10.3, 7.0 Hz, H₂C=CH), 5.03-4.96 (2 H, m, H ₂C=CH), 3.64 (2 H, t, J = 6.5 Hz, CH ₂OH), 2.03 (2 H, t, J = 6.0 Hz, CH ₂CH=CH₂), 1.55 (2 H, app quintet, J = 6.5 Hz, C2H₂), 1.46-1.20 (12 H, m, OH, C5H, 5 × CH₂), 0.89 (3 H, t, J = 6.5 Hz, CH₃). ¹³C NMR (75 MHz, CDCl₃): δ = 137.7 (H₂C=CH), 115.8 (H₂ C=CH), 63.2 (C1H₂), 38.2 (CH₂CH=CH₂), 37.5 (C5H), 33.3 (CH₂), 33.3 (CH₂), 33.2 (CH₂), 29.1 (CH₂CH₂CH₃), 23.2 (CH₂), 23.0 (CH₂), 14.3 (CH₃). HRMS (ES): m/z calcd for C₁₂H₂₄ONa [M + Na]⁺: 207.1725. Found: 207.1719.
Compound 13: IR (neat): 3075, 2928, 2858, 1639, 1589, 1508 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 6.40 (2 H, s, 2 ArH), 5.80 (1 H, ddt, J = 17.1, 10.3, 6.8 Hz, H₂C=CH), 4.92-4.83 (2 H, m, H ₂C=CH), 3.86 (6 H, s, 2 m-CH₃O), 3.83 (3 H, s, p-CH₃O), 2.56 (2 H, dd, J = 9.4, 6.4 Hz, CH ₂Ar), 2.11 (2 H, t, J = 6.4 Hz, CH ₂CH=CH₂), 1.48-1.37 (2 H, m, CH ₂CH₂Ar), 1.35-1.26 (1 H, m, CH), 1.22-1.08 (6 H, m, 3 × CH₂), 0.91 (3 H, t, J = 6.8 Hz, CH₃). ¹³C NMR (75 MHz, CDCl₃): δ = 153.1 (2 COCH₃, Ar ring), 139.0 (C, Ar ring), 137.4 (H₂C=CH), 136.0 (COCH₃, Ar ring), 116.0 (H₂ C=CH), 105.2 (2 CH, Ar ring), 61.0 (CH₃O), 56.1 (2 CH₃O), 38.1 (CH₂CH=CH₂), 37.2 (CHCH₂CH=CH₂), 35.4 (CH₂CH₂Ar), 33.7 (CH₂Ar), 33.1 (CH₂CH₂CH₂CH₃), 29.0 (CH₂CH₂CH₃), 23.2 (CH₂CH₃), 14.3 (CH₃). HRMS (ES): m/z calcd for C₁₉H₃₁O₃ [M + H]⁺: 307.2273. Found: 307.2281.
Compound 18a: [α]_D +12.3 (c 0.70, CHCl₃). IR (neat): 2955, 2927, 2826, 1459, 1378, 1186, 1103 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.69 (1 H, dd, J = 10.7, 2.6 Hz, C1H _AH_B), 3.50 (1 H, dd, J = 10.9, 3.6 Hz, C1H_A H _B), 3.50-3.36 (2 H, m, C2H and C4H), 3.46 (3 H, s, CH₃O), 3.42 (3 H, s, CH₃O), 3.40 (3 H, s, CH₃O), 3.39 (3 H, s, CH₃O), 3.24 (1 H, dd, J = 7.7, 3.0 Hz, C3H), 1.65 (1 H, ddd, J = 13.3, 7.7, 6.0 Hz, C5H _AH_B), 1.62-1.53 (1 H, m, C6H), 1.37-1.10 (7 H, m, C5H_A H _B and 3 × CH₂), 0.92 (3 H, d, J = 6.4 Hz, CH ₃C6H), 0.89 (3 H, t, J = 6.4 Hz, C10H₃). ¹³C NMR (75 MHz, CDCl₃): δ = 81.7 (C3H), 79.8 (C2H), 78.4 (C4H), 70.3 (C1H₂), 61.0 (CH₃O), 59.2 (CH₃O), 58.8 (CH₃O), 57.5 (CH₃O), 38.5 (C5H₂), 37.3 (C7H₂), 29.5 (C6H), 29.3 (C8H₂), 23.2 (C9H₂), 20.1 (CH₃C6H), 14.3 (C10H₃). HRMS (ES): m/z calcd for C₁₅H₃₂O₄Na [M + Na]⁺: 299.2198. Found: 299.2190.
Compound 18b: IR (neat): 2955, 2927, 2826, 1462, 1377, 1186, 1103 cm^-1. ¹H NMR (500 MHz, CDCl₃): δ = 3.72 (1 H, dd, J = 10.3, 2.1 Hz, C1H _AH_B), 3.51 (1 H, dd, J = 10.7, 3.4 Hz, C1H_A H _B), 3.49-3.36 (2 H, m, C2H and C4H), 3.46 (3 H, s, CH₃O), 3.42 (3 H, s, CH₃O), 3.40 (3 H, s, CH₃O), 3.37 (3 H, s, CH₃O), 3.26 (1 H, dd, J = 7.7, 2.1 Hz, C3H), 1.59 (1 H, ddd, J = 13.3, 8.1, 4.7 Hz, C5H _AH_B), 1.57-1.46 (1 H, m, C6H), 1.42 (1 H, ddd, J = 13.7, 8.5, 6.0 Hz, C5H_A H _B), 1.39-1.13 (6 H, m, 3 × CH₂), 0.91 (3 H, d, J = 6.4 Hz, CH ₃C6H), 0.89 (3 H, t, J = 6.8 Hz, C10H₃). ¹³C NMR (75 MHz, CDCl₃): δ = 80.3 (C3H), 79.6 (C2H), 78.4 (C4H), 70.2 (C1H₂), 61.0 (CH₃O), 59.2 (CH₃O), 58.0 (CH₃O), 57.6 (CH₃O), 37.5 (C7H₂), 37.1 (C5H₂), 29.5 (C6H), 29.3 (C8H₂), 23.1 (C9H₂), 20.2 (CH₃C6H), 14.3 (C10H₃). HRMS (ES): m/z calcd for C₁₅H₃₂O₄Na [M + Na]⁺: 299.2198. Found: 299.2197.