Stereoselective Synthesis of the C10–C18 Fragment of Iriomoteolide-3a

Chada Raji Reddy; Gajula Dharmapuri

doi:10.1055/s-0032-1318141

Synthesis, Table of Contents

Synthesis 2013; 45(5): 673-677
DOI: 10.1055/s-0032-1318141

paper

Stereoselective Synthesis of the C10–C18 Fragment of Iriomoteolide-3a

Chada Raji Reddy*

Division of Natural Products Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India Fax: +91(40)27160512 Email: rajireddy@iict.res.in

,

Gajula Dharmapuri

Division of Natural Products Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India Fax: +91(40)27160512 Email: rajireddy@iict.res.in

› Author Affiliations

Abstract

All articles of this category

Abstract

An efficient synthesis of the highly stereogenic centered C10–C18 fragment of iriomoteolide-3a has been accomplished. Key steps include Sharpless asymmetric dihydroxylation and epoxidation for generation of the desired stereocenters.

Key words

macrolide - total synthesis - iriomoteolide-3a - ortho-Claisen rearrangement - Sharpless dihydroxylation

Full Text

References

References
1 Oguchi K, Tsuda M, Iwamoto R, Okamoto Y, Kobayashi J, Fukushi E, Kawabata J, Ozawa T, Masuda A, Kitaya Y, Omasa K. J. Org. Chem. 2008; 73: 1567
2 Cribiú R, Jäger C, Nevado C. Angew. Chem. Int. Ed. 2009; 48: 8780
3 Reddy ChR, Dharmapuri G, Rao NN. Org. Lett. 2009; 11: 5730
4 Zhang Y, Deng L, Zhao G. Org. Biomol. Chem. 2011; 9: 4518
5 Chang C.-Y. J. Chin. Chem. Soc. 2011; 58: 31

6a Reddy ChR, Rao NN. Tetrahedron Lett. 2009; 50: 2478
6b Reddy ChR, Rao NN. RSC Adv. 2012; 2: 7724
6c Reddy ChR, Rao NN. Eur. J. Org. Chem. 2012; 1819
6d Reddy ChR, Suman D, Rao NN. Synlett 2012; 23: 272

7a Singh OV, Han H. Org. Lett. 2007; 9: 4801
7b Lee AH. F, Chan AS. C, Li T. Tetrahedron 2003; 59: 833

8 Sinha SC, Bagchi AS, Keinan E. J. Am. Chem. Soc. 1995; 117: 1447

9a Evans AP, Roseman JD. Tetrahedron Lett. 1997; 38: 5249
9b Mandel AL, Bellosta V, Curran DP, Cossy J. Org. Lett. 2009; 11: 3282

10 Compound 13 was converted into a known compound 13a (Scheme 3). A comparison of specific rotations {observed for 13a: [α]_D ³⁰ +16.3 (c 1.0, CHCl₃), Lit.³: [α]_D ³⁰ +16.6 (c 1.0, CHCl₃)} showed that the enantiomeric excess in the Sharpless dihydroxylation was >95%, and also confirmed the exclusive formation of 13 from 12 (by NOE studies on 13a ¹²).
11 Mohapatra DK, Sahoo G, Sankar K, Gurjar MK. Tetrahedron: Asymmetry 2008; 19: 2123
12 NOE experiments were carried out on compound 13a and the enhancements are shown in Figure 2.
13 Reddy ChR, Rao NN. Tetrahedron Lett. 2010; 51: 5840
14 Munakata R, Katakai H, Ueki T, Kurosaka J, Takao KI, Tadano KI. J. Am. Chem. Soc. 2004; 126: 11254
15 Parikh JR, Doering WV. E. J. Am. Chem. Soc. 1967; 89: 5505

16a Katsuki T, Sharpless KB. J. Am. Chem. Soc. 1980; 102: 5974
16b Gao Y, Hanson RM, Klunder JM, Ko SY, Masamune H, Sharpless KB. J. Am. Chem. Soc. 1987; 109: 5765

Supplementary Material

Supporting Information