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Title: Total synthesis of alkyl citrate and resorcylate natural products
Author: Calo, Frederick
ISNI:       0000 0004 2683 6842
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2010
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The total synthesis of citrafungin A (i),1 the determination of the absolute stereochemistry2 of CJ-13,981 (ii) and CJ-13,982 (iii) and the formal total synthesis of (–)-trachyspic acid, by making lactone iv,3 were achieved from a common intermediate (v). [Diagram omitted] Dioxolanone v was prepared on a multigram scale starting from commercially available 4-benzyloxy-butyric acid using, as key steps, an enantioselective syn-aldol reaction of a chiral oxazolidinone and a diastereoselective Seebach alkylation of a 1,3-dioxolan-2-one derivative. [Diagram omitted] From dioxolanone v, citrafungin A (i) was synthesised in 13 steps, CJ-13,981 (ii) and CJ- 13,982 (iii) in 9 steps and the intermediate lactone (iv) for the formal synthesis of (–)-trachyspic acid in 5 steps. Based on our recent advances on resorcylates metabolites,4 we carried out the total synthesis of aigialomycin D (vi),5 a potent 14-membered resorcylic macrolide, without the need for phenol protection, using the C-acylation of a keto-dioxinone dianion (or monoanion), a cascade sequence consisting of ketene generation, alcohol (vii) trapping and aromatization, and ring closing metathesis. [Diagram omitted] References: (1) Calo, F.; Richardson, J.; Barrett, A. G. M. J. Org. Chem. 2008, 73, 9292. (2) Calo, F.; Bondke. A.; Richardson, J.; White, A. J. P.; Barrett, A. G. M. Tetrahedron Lett. 2009, 50, 3388. (3) Calo, F.; Richardson, J.; White, A. J. P.; Barrett, A. G. M. Tetrahedron Lett. 2009, 50, 1566. (4) Navarro, I.; Basset, J.-F.; Hebbe, S.; Major, S.; Barrett, A. G. M. J. Am. Chem. Soc. 2008, 130, 10293. (5) Calo, F.; Richardson, J.; Barrett, A. G. M. Org. Lett. 2009, 11, 4910-
Supervisor: Barrett, Anthony Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral