Sains Malaysiana 38(6)(2009): 869–872

 

A Study Towards the Total Synthesis of TAN1251B

(Kajian bagi Mensintesis TAN1251B Secara Menyeluruh)

 

Aznuzilawati Asari*

Department of Chemical Sciences, Faculty of Science and Technology

Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Malaysia

 

Christopher J. Hayes

School of Chemistry, University of Nottingham

University Park, Nottingham NG7 2RD, United Kingdom

 

Diserahkan: 18 Februari 2009 / Diterima: 20 April 2009

 

ABSTRACT

 

A synthetic route towards the synthesis of TAN1251B was developed utilizing an alkylidene carbene insertion reaction as a key step to construct the quartenary centre. The α-hydroxylation of the 5,6-spirocyclic enone with iodosobenzene was successful to give a mixture of diastereomer compounds 20 and 21 in 1:1.2 ratios.

 

Keywords: TAN1251B; alkylidene carbene; α-hydroxylation; iodosobenzene

 

ABSTRAK

 

Laluan sintetik bagi mensintesis sebatian TAN1251B dikembangkan dengan menggunakan tindak balas penyelitan alkilidin karbena sebagai langkah untuk menjana pusat kuarterner. Tindak balas penghidroksilan 5,6-spirosiklik enon dengan iodosobenzena telah berjaya memberikan campuran hasil diastereomer 20 dan 21 dalam nisbah 1:1.2.

 

Kata kunci: TAN1251B; alkiliden karbena; α-penghidroksilan; iodosobenzena

 

RUJUKAN

 

Asari, A., Angelov, P., Auty, J.M. & Hayes, C.J. 2007. Enantioselective Synthesis of the Tricyclic Core of (−)-FR901483. Tetrahedron Lett. 48: 2631.

Asnuzilawati Asari. 2007. Towards the Total Synthesis of (−)-FR901483 and (+)-TAN1251B. Thesis for Doctor of Philosophy, School of Chemistry, University of Nottingham.

Auty, J. M. A., Churcher, I. & Hayes, C. J. 2004. An Enantioselective Formal Total Synthesis of (-)-TAN1251A. Synlett. 8: 1443.

Mizutani, H., Takayama, J., Soeda, Y. & Honda, T. 2002. Facile Synthesis of Enantiopure (-)-TAN1251A. Tetrahedron Lett. 43: 2411.

Mizutani, H. Takayama, J. & Honda, T. 2005. Enantiospecific Total Synthesis of TAN1251C and TAN1251D. Synlett. 2: 328.

Moriarty, R.M., Duncan, M.P. & Prakash, O. 1987. Hypervalent Iodine in Synthesis. 78. Direct α-Hydroxylation of Ketones using [Hydroxy(tosyloxy)-iodo]benzene in Dimethyl Sulfoxide-water. J. Chem. Soc. Perkin Trans. 1. 1781

Moriarty, R. M., John, L. S. & Du, P. C. 1981a. Hypervalent Iodine in Organic Synthesis. A Novel Route to the Dihydroxyacetone Side-chain in the Pregnene Series. J. Chem. Soc. Chem. Comm. 641.

Moriarty, R.M., Hu, H. & Gupta, S.C. 1981b. Direct Hydroxylation of Ketones using Iodosobenzene. Tetrahedron Lett. 22(14): 1283.

Nagumo, S., Nishida, A., Yamazaki, C., Murashige, K. & Kawahara, N. 1998. Total Synthesis of TAN1251A. Tetrahedron Lett. 39: 4493.

Nagumo, S., Nishida, A. Yamazaki, C., Matoba, A., Murashige, K. & Kawahara, N. 2002. Total Synthesis of Antimuscarinic Alkaloid, (±)-TAN1251A. Tetrahedron 58: 4917.

Nagumo, S., Matoba, A. Ishii, Y., Yamaguchi, S., Akutsu, N., Nishijima, H, Nishida, A. & Kawahara, N. 2002. Synthesis of (−)-TAN1251A using 4-Hydroxy-L -Proline as a Chiral Source. Tetrahedron 58: 9871.

Ousmer, M., Braun, N. A., Bavoux, C., Perrin, M. & Ciufolini, M. A. 2001. Total Synthesis of Tricyclic Azaspirane Derivatives of Tyrosine: FR901483 and TAN1251C. J. Am. Chem. Soc. 123: 7534.

Shirafuji, H., Tubotoni, S., Ishimaru, T. & Harada, S. 1992. PCT Int. Appl. WO 9113. 887; Chem. Abstr. 1992. 116: 39780t.

Snider, B. B. & Lin, H. 2000. Facile Synthesis of Enantiopure (-)-TAN1251A. Org. Lett. 2(5): 643.

Wardrop, D. J. & Basak A. 2001. N-Methoxy-N-Acylnitrenium Ions: Application to the Formal Synthesis of (-)-TAN1251A. Org. Lett. 3(7): 1053.

 

 

*Pengarang untuk surat-menyurat; e-mail: asnu@umt.edu.my

 

 

 

sebelumnya