Bismuth(III) Chloride Catalyzed Efficient and Selective Cleavage of Trityl Ethers

Gowravaram Sabitha; E. Venkata Reddy; R. Swapna; N. Mallikarjun Reddy; J. S. Yadav

doi:10.1055/s-2004-825602

LETTER

Bismuth(III) Chloride Catalyzed Efficient and Selective Cleavage of Trityl Ethers [1]

Gowravaram Sabitha*, E. Venkata Reddy, R. Swapna, N. Mallikarjun Reddy, J. S. Yadav
Organic Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Fax: +91(40)27160512; e-Mail: sabitha@iict.ap.nic.in;

Abstract

All articles of this category

Abstract

A highly selective and efficient protocol has been developed for detritylation using 5 mol% BiCl₃ in acetonitrile. The cleavage proceeds at room temperature in high yields and the conditions are mild enough to tolerate a variety of acid-base sensitive functional groups.

Key words

trityl ethers - catalytic - selective - bismuth(III) chloride - alcohols

Full Text

References

IICT Communication No. 031004.

<A NAME="RD25403ST-2A">2a</A> Helferich B. Adv. Carbohydr. Chem. 1948, 3: 79

<A NAME="RD25403ST-2B">2b</A> Greene TW. Wuts PGM. Protective Groups in Organic Synthesis 2nd ed.: John Wiley and Sons; New York: 1999. p.102

<A NAME="RD25403ST-2C">2c</A> Kocienski PJ. Protecting Groups Thieme; Stuttgart, New York: 1994.

<A NAME="RD25403ST-3">3</A> Dekker CA. Goodman L. In The Carbohydrate Chemistry and Biochemistry Vol IIA: Pigman W. Horton D. Academic Press; New York and London: 1970. p.22-28

<A NAME="RD25403ST-4">4</A> Bessodes M. Komiotis D. Antonakis K. Tetrahedron Lett. 1986, 27: 579

<A NAME="RD25403ST-5">5</A> Micheel F. Chem. Ber. 1932, 65: 262

<A NAME="RD25403ST-6A">6a</A> Helferich B. Kelein M. Ann. 1926, 450: 219

<A NAME="RD25403ST-6B">6b</A> Choy YM. Unrau AM. Carbohydr. Res. 1971, 17: 439

<A NAME="RD25403ST-6C">6c</A> Yung NC. Fox JJ. J. Am. Chem. Soc. 1961, 83: 3060

<A NAME="RD25403ST-7">7</A> MacCoss M. Cameron DJ. Carbohydr. Res. 1978, 60: 206

<A NAME="RD25403ST-8A">8a</A> Kohli V. Blocker H. Koster H. Tetrahedron Lett. 1980, 21: 2683

<A NAME="RD25403ST-8B">8b</A> Matteucci MD. Caruthers MH. Tetrahedron Lett. 1980, 21: 3243

<A NAME="RD25403ST-9">9</A> Koster H. Sinha ND. Tetrahedron Lett. 1982, 23: 2641

<A NAME="RD25403ST-10">10</A> Lu RJ. Liu D. Giese RW. Tetrahedron Lett. 2000, 41: 2817

<A NAME="RD25403ST-11">11</A> Ali K.-N. Alamdari RF. Tetrahedron 2001, 57: 6805

<A NAME="RD25403ST-12">12</A> Yadav JS. Reddy BVS. Synlett 2000, 1275

<A NAME="RD25403ST-13">13</A> Wahlstrom JL. Ronald C. J. Org. Chem. 1998, 63: 6021

<A NAME="RD25403ST-14">14</A> Imagawa H. Tsuchihashi T. Singh RK. Yamamoto H. Sugihara T. Nishizawa M. Org. Lett. 2003, 5: 153

<A NAME="RD25403ST-15">15</A> Leonard NM. Wieland LC. Mohan RS. Tetrahedron 2002, 58: 8373

<A NAME="RD25403ST-16A">16a</A> Sabitha G. Babu RS. Reddy EV. Yadav JS. Chem. Lett. 2000, 9: 1074

<A NAME="RD25403ST-16B">16b</A> Sabitha G. Babu RS. Reddy EV. Srividya R. Yadav JS. Adv. Synth. Catal. 2001, 343: 169

<A NAME="RD25403ST-16C">16c</A> Sabitha G. Venkata Reddy E. Yadav JS. Rama Krishna KVS. Ravi Sankar A. Tetrahedron Lett. 2002, 43: 4029

<A NAME="RD25403ST-16D">16d</A> Tetrahydrochromano[4,3-b]-quinolines: Sabitha G. Venkata Reddy E. Yadav JS. Synthesis 2001, 1979

<A NAME="RD25403ST-16E">16e</A> Hexahydrodibenzo[b,h][1,6]-naphthyridines: Sabitha G. Venkata Reddy E. Maruthi Ch. Yadav JS. Tetrahedron Lett. 2002, 43: 1573

<A NAME="RD25403ST-16F">16f</A> Octahydroacridines: Sabitha G. Venkata Reddy E. Yadav JS. Synthesis 2002, 409

<A NAME="RD25403ST-16G">16g</A> Sabitha G. Srinivas Reddy C. Maruthi C. Venkata Reddy E. Yadav JS. Synth. Commun. 2003, 33(17): 306

General Procedure. Trityl ether (2 mmol) in dry MeCN (2 mL), was treated with a catalytic amount of BiCl₃ (5 mol%) and stirred at r.t. After complete conversion of the reaction as indicated by TLC, the reaction mixture was filtered through a small pad of Celite. The filtrate was extracted with EtOAc, washed with brine and dried over anhyd Na₂SO₄. After evaporation, the residue was purified by column chromatography using silica gel (60-120 mesh; hexane-EtOAc) to furnish pure alcohol.
Spectroscopic data for selected compounds. Compound 1a: IR (neat): 2941, 1057, 749 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.92-2.12 (m, 2 H), 2.72 (t, 2 H, J = 10.0 Hz), 3.17 (t, 2 H, J = 5.1 Hz), 7.12-7.35 (m, 15 H), 7.47 (d, 6 H, J = 8.2 Hz). MS: m/z = 378 [M⁺]. Compound 2a: IR (neat): 3355, 2943, 1057, 745 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.92-2.12 (m, 2 H), 2.72 (t, 2 H, J = 5.2 Hz), 3.63 (t, 2 H, J = 9.8 Hz), 7.15-7.25 (m, 5 H). MS: m/z = 136 [M⁺]. Compound 1d: IR (neat): 2358, 1219, 1109, 773 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.03 (s, 9 H), 1.38 (s, 2 H), 1.51-1.62 (m, 4 H), 3.02 (t, 2 H, J = 5.9 Hz), 3.62 (t, 3 H, J = 5.2 Hz), 7.16-7.41 (m, 19 H), 7.39 (d, 6 H, J = 7.9 Hz). MS: m/z = 585 [M⁺]. Compound 2d: IR (neat): 3332, 2855, 1104, 1028, 772 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.03 (s, 9 H), 1.39-1.59 (m, 6 H), 3.59 (t, 2 H, J = 6.0 Hz), 3.64 (t, 2 H, J = 6.0 Hz), 7.33-7.38 (m, 2 H), 7.62 (d, 2 H, J = 7.3 Hz). MS: m/z = 342 [M⁺]. Compound 1e: IR (neat): 2936, 1727, 1156, 1071 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.19 (s, 9 H), 1.46-1.71 (m, 6 H), 3.06 (t, 2 H, J = 5.9 Hz), 4.03 (t, 2 H, J = 5.9 Hz), 7.18-7.33 (m, 9 H), 7.45 (d, 6 H, J = 8.2 Hz). MS: m/z = 430 [M⁺]. Compound 2e: IR (neat): 3439, 2938, 1728, 1159, 1057 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.18 (s, 9 H), 1.38-1.72 (m, 6 H), 3.62 (t, 2 H, J = 6.6 Hz), 4.04 (t, 2 H, J = 6.6 Hz). MS: m/z = 188 [M⁺]. Compound 1i: IR (neat): 2361, 1219, 1174, 1060, 771 cm^{- 1}. ¹H NMR (200 MHz, CDCl₃): δ = 3.60 (d, 2 H, J = 6.6 Hz), 3.80 (s, 3 H), 3.85 (d, 2 H, J = 6.5 Hz), 4.30 (s, 2 H), 5.60-5.90 (m, 2 H), 6.76 (d, 2 H, J = 8.2 Hz), 7.15 (d, 2 H, J = 8.1 Hz), 7.30 (m, 9 H), 7.45 (d, 6 H, J = 8.2 Hz). MS: m/z = 450 [M⁺]. Compound 2i: IR (neat): 3418, 2935, 1514, 1174, 1032 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 3.80 (s, 3 H), 4.01 (d, 2 H, J = 6.5 Hz), 4.15 (d, 2 H, J = 6.5 Hz), 4.40 (s, 2 H), 5.50-5.90 (m, 2 H), 6.85 (d, 2 H, J = 8.2 Hz), 7.27 (d, 2 H, J = 8.2 Hz). MS: m/z = 208 [M⁺]. Compound 1n: IR (neat): 2985, 2935, 1611, 1509, 1216, 1077 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.31 (s, 6 H), 1.45 (s, 3 H), 1.53 (s, 3 H), 3.50-3.63 (m, 2 H), 3.90 (dt, 1 H, J = 6.0 and 2.3 Hz), 4.20-4.30 (m, 2 H), 4.48-4.58 (m, 2 H), 5.50 (d, 1 H, J = 5.1 Hz), 7.20 (m, 9 H), 7.40 (d, 6 H, J = 7.3 Hz). MS: m/z = 503 [M⁺]. Compound 2n: IR (neat): 3425, 2980, 2930, 1509, 1077 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.31 (s, 6 H), 1.45 (s, 3 H), 1.53 (s, 3 H), 3.60-3.73 (m, 2 H), 3.80 (dt, 1 H, J = 6.0 and 2.3 Hz), 4.20-4.30 (m, 2 H), 4.48-4.58 (m, 2 H), 5.50 (d, 1 H, J = 5.1 Hz). MS: m/z = 260 [M⁺].

<A NAME="RD25403ST-18">18</A> Swamy NR. Venkateswarlu Y. Tetrahedron Lett. 2002, 43: 7549