Lithium carbenoids induced ring enlargement of silacyclobutane into 2-halo-1-silacyclopentane and its use in organic synthesis

Matsumoto, Kozo; Aoki, Yasuhiko; Oshima, Koichiro; Utimoto, Kiitirô; Rahman, Noorsaadah Abd.

doi:10.1016/s0040-4020(01)96257-x

Cited by 38 publications

(6 citation statements)

References 24 publications

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“…The combined organic layer was dried over Na 2 SO 4 and evaporated. The crude product was chromatographed on silica gel (hexane−AcOEt, 10:1) to give trans -2-butyl-3-dimethylphenylsilyltetrahydropyran ( trans - 2a , 103 mg, 75%) and a mixture of ( E )-4-nonen-1-ol ( 4 , 15%) and 1a (6%, Z / E = 83/17). trans - 2a : bp 140 °C (0.30 Torr, bath temp); IR (neat) 2950, 1458, 1428, 1377, 1249, 1104, 731, 699 cm -1 ; 1 H NMR (CDCl 3 ) δ 0.28 (s, 3H), 0.31 (s, 3H), 0.78 (t, J = 6.9 Hz, 3H), 1.03−1.59 (m, 10H), 1.70−1.79 (m, 1H), 3.20 (ddd, J = 10.6, 7.9, 2.5 Hz, 1H), 3.36 (td, J = 10.9, 3.6 Hz, 1H), 3.92−4.00 (m, 1H), 7.32−7.38 (m, 3H), 7.44−7.53 (m, 2H); 13 C NMR (CDCl 3 ) δ −3.66 (CH 3 ), −3.29 (CH 3 ), 13.98 (CH 3 ), 22.57 (CH 2 ), 25.93 (CH 2 ), 27.41 (CH 2 × 2), 30.05 (CH), 36.07 (CH 2 ), 68.38 (CH 2 ), 79.70 (CH), 127.71 (CH × 2), 128.84 (CH), 133.75 (CH × 2), 138.62 (C); MS m / z (relative intensity) 276 (M + , 0.6), 135 (100).…”

Section: Methodsmentioning

confidence: 99%

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹

et al. 2002

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Acid-catalyzed intramolecular addition of a hydroxy group to alpha-alkylated vinylsilanes has been studied. Treatment of (Z)-5-alkyl-5-silyl-4-penten-1-ols 1 (R = alkyl) with 5 mol % TiCl(4) in CHCl(3) gave trans-2-alkyl-3-silyltetrahydropyrans 2 exclusively (trans/cis = >99/1 to 97/3). The cyclization efficiency and rate strongly depended on the geometry of the C-C double bond and the silyl group. The use of (E)-vinylsilanes resulted in lower yields with poor cis-selectivity. In the cyclization of (Z)-1 (R = Bu), the silyl group used, the reaction time, and the yield of 2 were as follows: SiMe(2)Ph, 9.5 h, 75%; SiMe(3), 7.5 h, 66%; SiMePh(2), 24 h, 58%; SiMe(2)-t-Bu, 0.75 h, 85%; SiMe(2)Bn, 1.5 h, 78%. This 1,2-silyl-migrative cyclization could be applied to stereoselective synthesis of trisubstituted tetrahydropyrans. The acid-catalyzed reaction of 1-, 2-, or 3-substituted (Z)-5-silyl-4-nonen-1-ols 8 gave r-2,t-3,c-6-, r-2,t-3,t-5-, or r-2,t-3,c-4-trisubstituted tetrahydropyrans with high diastereoselectivity, respectively. (Z)-4-Alkyl-4-silyl-3-buten-1-ols 5 as well as 1 underwent the 1,2-silyl-migrative cyclization to give 2-alkyl-3-silyltetrahydrofurans 6 with high trans-selectivity. This silicon-directed cyclization was also available for the stereoselective synthesis of tri- and tetrasubstituted tetrahydrofurans.

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Section: Methodsmentioning

confidence: 99%

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹

et al. 2002

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“…Ando et al [27] reported carboalkoxycarbenes insertion into SiC bonds later. Oshima and coworkers [28][29][30] developed this ring expansion of siletane into an efficient method to synthesize various five-and sixmembered silacycles with less toxic alkali metals (Scheme 2). Later, Sakurai and co-workers [31] developed a similar carbene insertion reaction to synthesize silepine 11 (eq.…”

Section: Metal-mediated Silacycle Formation Via Si-c Bond Cleavagementioning

confidence: 99%

Formation of silacycles via metal-mediated or catalyzed Si-C bond cleavage

Wang

Duan

2012

Chin. Sci. Bull.

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Silacycles play a very important role in modern organic chemistry and materials science. Construction of silacyclic skeletons via metal-mediated or catalyzed Si-C bond cleavage has attracted much recent attention. Several interesting and useful synthetic strategies have been reported in the literature. In this review, we have summarized recent developments on metal-mediated or catalyzed Si-C bond cleavage, which lead to the synthesis of silacycles, including silacyclobutenes, silacyclopentanes, silacyclopentadienes (siloles), 6-membered silacycles, and their derivatives.

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“…Reactions of siletanes with carbenoids of type CHX 2 Li lead to the formation of silacyclopentane derivatives (Scheme 3.237) [421]. Ring expansions are also observed by reaction of 1-(1-iodoalkyl)siletanes with MeLi, t BuOK or AgOAc and by reaction of 1-oxiranylsiletanes with MeLi (Scheme 3.237) [422].…”

Section: Reactivitymentioning

confidence: 99%

Four‐Membered Heterocycles: Structure and Reactivity

Rousseau

Robin

2011

Modern Heterocyclic Chemistry

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Lithium carbenoids induced ring enlargement of silacyclobutane into 2-halo-1-silacyclopentane and its use in organic synthesis

Cited by 38 publications

References 24 publications

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹

Formation of silacycles via metal-mediated or catalyzed Si-C bond cleavage

Four‐Membered Heterocycles: Structure and Reactivity

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Lithium carbenoids induced ring enlargement of silacyclobutane into 2-halo-1-silacyclopentane and its use in organic synthesis

Cited by 38 publications

References 24 publications

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans1

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans1

Formation of silacycles via metal-mediated or catalyzed Si-C bond cleavage

Four‐Membered Heterocycles: Structure and Reactivity

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1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹

1,2-Silyl-Migrative Cyclization of Vinylsilanes Bearing a Hydroxy Group: Stereoselective Synthesis of Multisubstituted Tetrahydropyrans and Tetrahydrofurans¹