Paterson’s total synthesis

Since its introduction by Allred and Liebsekind in 1996 [114], copper thiophene-2-carboxylate (CuTC) has emerged as a mild and useful reagent for mediating the cross-coupling of organostannanes with vinyl iodides at room temperature. CuTC is especially effective for substrates that are not stable at high temperature. In Paterson s total synthesis of elaiolide, he enlisted a CuTC-promoted Stille cyclodimerization of vinyl iodide 131 to afford the 16-membered macrocycle 132 under very mild conditions [115]. 

Scheme 4. (a) Chiral auxiliaries in the form of a-oxygenated substrates to accomplish 1,2-anf/ aldol stereoselectivity in Paterson s total synthesis of ACRL Toxin IIIB (42) and (b) methods to remove the directing group. (1994) ... 

Scheme 5. Use of three different approaches for aldol stereoselectivity in Paterson s total synthesis of ebelactones A and B (61 and 62). (1990) ...

Scheme 20. Final stages and completion of Paterson s total synthesis of swinholide A (1).

The outstanding diastereoselectivity in these reactions is further demonstrated in Paterson s total synthesis of the potential antiviral agent (+)-... 

This chapter attempts to recount some of the highs and lows encountered during the Paterson group s total synthesis of spongistatin 1/altohyrtin A, an extremely rare marine macrolide with a seductively complex structure in combination with displaying promising anticancer properties. We provide the reader with an emotional roller coaster ride through a project that spanned some 7 years, with early studies aimed at... 

Yeung K-S, Paterson I (2005) Advances in the Total Synthesis of Biologically Important Marine Macrolides. Chem Rev 105 4237... 

Since Leighton s first total synthesis, total syntheses of leucascandrolide A have been achieved by Rychnovsky (formal), Carreira, Wipf (formal), Kozmin (racemic), Paterson, Williams (formal), Crimmins (formal), and Panek. In this section, these syntheses are briefly introduced. 

Nakata T (2002) Total synthesis of macrolides. In Omura S (ed) Macrolide antibiotics. Academic Press, San Diego, chap 4 Norcross RD, Paterson I (1995) Chem Rev 95 2041 Yeung KS, Paterson I (2002) Angew Chem Int Ed 41 4632 Kobayashi J, Tsuda M (2004) Nat Prod Rep 21 77 Boivin TLB (1987) Tetrahedron 43 3309 Gonzalez MA, Pattenden G (2003) Angew Chem Int Ed 42 1255 Pattenden G, Gonzalez MA, Little PB, Millan DS, Plowright AT, Tornos JA, Ye T (2003) Org Biomol Chem 1 4173... 

Scheme 4.67 Diisopinocampheylboranes 292 as controllers in Paterson s aldol procedure. Application in a total synthesis of swinholide A.

Advances in the total synthesis of biologically important marine macrolides. Yeung, K.-S., Paterson, I. (2005), Chem. Rev., 105, 4237-4313. 

Paterson, I., Yeung, K.S., Watson, C., Ward, R.A., and Wallace, PA. (1998a) The total synthesis of scytophycin C - Part 1 - stereocontroHed synthesis of the Ci-Cj2 protected seco acid. Tetrahedron, 54, 11935-11954. 

Paterson, I. and Wren, S.P. (1993) Studies towards the total synthesis of the marine-derived immunosuppressant discodermolide asymmetric synthesis of a C1-C8 6-lactone subunit. J. Chem. Soc. Chem. Commun., 1790-1792. 

Mickel, S.J., Daeffler, R and Prikoszovich, W. (2005) A study of the Paterson boron aldol reaction as used in the large-scale total synthesis of the anticancer marine natural product (+)-discode-rmolide. Org. Process Res. Dev., 9,113-120. 

Mulzer, J., Meyer, F., Buschmann, J., and Luger, P. (1995) Asymmetric synthesis of the C-26-C-32 tetrahydropyran moiety of swinholide A by hetero-Diels—Alder reaction. Tetrahedron Lett., 36, 3503—3506. Paterson, 1., Gumming, J.G., Ward, R.A., and Lamboley, S. (1995) The total synthesis of swinholide A. 1. A stereocontrolled synthesis of a C19-C32 segment. Tetrahedron, 51, 9393-9412. 

---