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Synlett 2005(1): 167-169  
DOI: 10.1055/s-2004-836045
LETTER
© Georg Thieme Verlag Stuttgart · New York

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;
Further Information

Publication History

Received 12 October 2004
Publication Date:
29 November 2004 (online)

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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

    References

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8

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).

12

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

27

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 AHB), 3.50 (1 H, dd, J = 10.9, 3.6 Hz, C1HA 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 AHB), 1.62-1.53 (1 H, m, C6H), 1.37-1.10 (7 H, m, C5HA 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 AHB), 3.51 (1 H, dd, J = 10.7, 3.4 Hz, C1HA 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 AHB), 1.57-1.46 (1 H, m, C6H), 1.42 (1 H, ddd, J = 13.7, 8.5, 6.0 Hz, C5HA 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.