A New Protocol for Selective
Cleavage of Acyl Protecting Groups in 2′-O-Modified 3′,5′-O-(Tetraisopropyldisiloxane-1,3-diyl)ribonucleosides

M. S. Drenichev; I. V. Kulikova; G. V. Bobkov; V. I. Tararov; S. N. Mikhailov

doi:10.1055/s-0030-1258270

PAPER

A New Protocol for Selective Cleavage of Acyl Protecting Groups in 2′-O-Modified 3′,5′-O-(Tetraisopropyldisiloxane-1,3-diyl)ribonucleosides

M. S. Drenichev, I. V. Kulikova, G. V. Bobkov, V. I. Tararov, S. N. Mikhailov*
Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, Vavilov str. 32, Moscow 119991, Russian Federation
Fax: +7(499)1351405; e-Mail: smikh@eimb.ru;

Abstract

All articles of this category

Abstract

The stability of tetraisopropyldisiloxane-1,3-diyl (TIPDS) protection in nucleosides in ammonia/amine solutions in methanol and ethanol was studied. In ammonia-methanol at ambient temperature significant partial cleavage of TIPDS was observed. When ethanol was used instead of methanol this undesired side reaction was completely inhibited. It was found that commercially available 8 M methylamine-ethanol solution is the reagent of choice for selective deacylation of N- or/and O-acyl protected nucleosides without notable cleavage of 3′,5′-TIPDS group. Several examples of the developed protocol for the preparation 2′-O-modified nucleosides with overall high yields are presented.

Key words

nucleosides - blocking group stability - tetraisopropyldisiloxane-1,3-diyl - protecting group - N-deacylation - O-deacylation

Full Text

References

<A NAME="RP10510SS-1">1</A> Markiewicz WT. J. Chem. Res., Synop. 1979, 24

<A NAME="RP10510SS-2">2</A> Robins MJ. Wilson JS. Hansske F. J. Am. Chem. Soc. 1983, 105: 4059

<A NAME="RP10510SS-3">3</A> Hansske F. Madej D. Robins MJ. Tetrahedron 1984, 40: 125

<A NAME="RP10510SS-4">4</A> Sproat BS. Beijer B. Iribarren A. Nucleic Acids Res. 1990, 18: 41

<A NAME="RP10510SS-5">5</A> Cuenoud B. Casset F. Husken D. Natt F. Wolf RM. Altman K.-H. Martin P. Moser HE. Angew. Chem. Int. Ed. 1998, 37: 1288

<A NAME="RP10510SS-6">6</A> Kawasaki AM. Casper MD. Prakash TP. Manalili S. Sasmor H. Manoharan M. Cool DP. Tetrahedron Lett. 1999, 40: 661

<A NAME="RP10510SS-7">7</A> Mikhailov SN. Efimtseva EV. Gurskaya GV. Zavodnik VE. De Bruyn A. Rozenski J. Herdewijn P. J. Carbohydr. Chem. 1997, 16: 75

<A NAME="RP10510SS-8">8</A> Markiewicz WT. Niewczyk A. Gdaniec Z. Adamiak DA. Dauter Z. Rypniewski W. Chmielewski M. Nucleosides Nucleotides 1998, 17: 411

<A NAME="RP10510SS-9">9</A> Efimtseva EV. Bobkov GV. Mikhailov SN. Van Aerschot A. Schepers G. Busson R. Rozenski J. Herdewijn P. Helv. Chim. Acta 2001, 84: 2387

<A NAME="RP10510SS-10">10</A> Bobkov GV. Brilliantov KV. Mikhailov SN. Rozenski J. Van Aerschot A. Herdewijn P. Collect. Czech. Chem. Commun. 2006, 71: 804

<A NAME="RP10510SS-11">11</A> Mikhailov SN. Kulikova IV. Nauwelaerts K. Herdewijn P. Tetrahedron 2008, 64: 2871

<A NAME="RP10510SS-12">12</A> Bobkov GV. Mikhailov SN. Van Aerschot A. Herdewijn P. Tetrahedron 2008, 64: 6238

<A NAME="RP10510SS-13">13</A> Scaringe SA. Methods Enzymol. 2000, 317: 3

<A NAME="RP10510SS-14">14</A> Saneyoshi H. Seio K. Sekine M. J. Org. Chem. 2005, 70: 10453

<A NAME="RP10510SS-15">15</A> Semenyuk A. Foldesi A. Johansson T. Estmer-Nilsson C. Blomgren P. Brannvall M. Kirsebom LA. Kwiatkowski M. J. Am. Chem. Soc. 2006, 128: 12356

<A NAME="RP10510SS-16">16</A> Cieslak J. Kauffman JS. Kolodziejski MJ. Lloyd JR. Beaucage SL. Org. Lett. 2007, 9: 671

<A NAME="RP10510SS-17">17</A> Parey N. Baraguey C. Vasseur J.-J. Debart F. Org. Lett. 2006, 8: 3869

<A NAME="RP10510SS-18">18</A> Shiba Y. Masuda H. Watanabe N. Ego T. Takagaki K. Ishiyama K. Ohgi T. Yano J. Nucleic Acids Res. 2007, 35: 3287

<A NAME="RP10510SS-19">19</A> Robins MJ. Hawrelak SD. Hernandez AE. Wnuk SF. Nucleosides Nucleotides 1992, 11: 821

<A NAME="RP10510SS-20">20</A> Karpeisky A. Sweedler D. Haeberli P. Read J. Jarvis K. Beigelman L. Bioorg. Med. Chem. Lett. 2002, 12: 3345

<A NAME="RP10510SS-21A">21a</A> Kocieński PJ. Protecting Groups Georg Thieme Verlag; Stuttgart: 2005. p.171-173

<A NAME="RP10510SS-21B">21b</A> Wuts PGM. Greene TW. Greene’s Protective Groups in Organic Synthesis J. Wiley & Sons; Hoboken: 2007. p.356-360

<A NAME="RP10510SS-22">22</A> Robins MJ. Wilson JS. Sawyer L. James MNG. Can. J. Chem. 1983, 61: 1911

<A NAME="RP10510SS-23">23</A> Efimtseva EV. Mikhailov SN. Biochemistry (Moscow) 2002, 67: 1136

<A NAME="RP10510SS-24">24</A> Efimtseva EV. Mikhailov SN. Russ. Chem. Rev. (Engl. Transl.) 2004, 73: 401

<A NAME="RP10510SS-25">25</A> Efimtseva EV. Kulikova IV. Mikhailov SN. Curr. Org. Chem. 2007, 11: 337

<A NAME="RP10510SS-26">26</A> Efimtseva EV. Kulikova IV. Mikhailov SN. Molecular Biology (Moscow) 2009, 43: 301

<A NAME="RP10510SS-27">27</A> Verdegaal CHM. Jansse PL. de Rooij JFM. van Boom JH. Tetrahedron Lett. 1980, 21: 1571

<A NAME="RP10510SS-28">28</A> Markiewicz WT. Bartoszuk A. Bull. Pol. Acad. Sci. 1984, 32: 453

<A NAME="RP10510SS-29">29</A> Kulikova IV. Muradova DA. Mikhailov SN. ARKIVOC 2009, (iii): 158

<A NAME="RP10510SS-30">30</A> Chow S. Wen K. Sanghvi YS. Theodorakis EA. Nucleosides, Nucleotides Nucleic Acids 2003, 22: 583

<A NAME="RP10510SS-31">31</A> McBride LJ. Kierzek R. Beaucage SL. Caruthers MH. J. Am. Chem. Soc. 1986, 108: 2040

<A NAME="RP10510SS-32">32</A> Jagtap P. Szabó C. Nat. Rev. Drug Discovery 2005, 4: 421

<A NAME="RP10510SS-33">33</A> Curtin NJ. Expert Rev. Mol. Med. 2005, 7: 1

<A NAME="RP10510SS-34">34</A> Gottlieb HE. Kotlyar V. Nudelman A. J. Org. Chem. 1997, 62: 7512