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Isolation of Pyrrolocins A-C: cis- and trans-Decalin Tetramic Acid Antibiotics from an Endophytic Fungal-Derived Pathway

Raquel C. Jadulco,† Michael Koch,

† Thomas B. Kakule,

‡ Eric W. Schmidt,

‡ Anita Orendt,

∆ Haiyin He,

§ Jeffrey E. Janso,

§ Guy T.

Carter,ǁ Erica C. Larson,

† Christopher Pond,

† Teatulohi K. Matainaho,

┴ and Louis R. Barrows

†┴*

†Department of Pharmacology and Toxicology, University of Utah, Salt Lake City, Utah, USA

‡Department of Medicinal Chemistry, University of Utah, Salt Lake City, Utah, USA

∆ Center for High Performance Computing, University of Utah, Salt Lake City, Utah, USA

§Natural Products – Worldwide Medicinal Chemistry, Pfizer Worldwide Research and Development, 445 Eastern Point Road, Groton,

Connecticut 06340, USA

ǁCarter-Bernan Consulting, 350 Phillips Hill Road, New City, NY 10956 , USA

┴School of Medicine and Health Sciences, University of Papua New Guinea, Boroko, NCD, Papua New Guinea

*Email: lbarrows@pharm.utah.edu. Phone: (801) 5824547. Fax (801) 5855111

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List of supporting information

No. Content Page

S1 1H NMR of Compound 1 in DMSO-d6 at 400 MHz. 3

S2 13

C NMR of Compound 1 in DMSO-d6 at 100 MHz. 4

S3 COSY of Compound 1 in DMSO-d6 at 400 MHz. 5

S4 HSQC of Compound 1 in DMSO-d6 at 400 MHz. 6

S5 HMBC of Compound 1 in DMSO-d6 at 400 MHz. 7

S6 ROESY of Compound 1 in DMSO-d6 at 400 MHz. 8

S7 1H NMR of Compound 2 in CD3OD at 500 MHz. 9

S8 13

C NMR of Compound 2 in CD3OD at 125 MHz. 10

S9 COSY of Compound 2 in DMSO-d6 at 500 MHz. 11

S10 ROESY of Compound 2 in DMSO-d6 at 500 MHz. 12

S11 HMBC of Compound 2 in DMSO-d6 at 500 MHz. 13

S12 HSQC of Compound 2 in DMSO-d6 at 500 MHz 14

S13 1H NMR of Compound 3 in DMSO-d6 at 500 MHz 15

S14 13

C NMR of Compound 3 in DMSO-d6 at 125 MHz 16

S15 COSY of Compound 3 in DMSO-d6 at 500 MHz. 17

S16 HMBC of Compound 3 in DMSO-d6 at 500 MHz 18

S17 HSQC of Compound 3 in DMSO-d6 at 500 MHz 19

S18 ROESY of Compound 3 in DMSO-d6 at 500 MHz 20

S19 Relevant part of the HPLC chromatogram of hydrolytic product serine-FDLA (HPS-FDLA) co-

injected with D-serine-FDLA

21

S20 Relevant part of the HPLC chromatogram of hydrolytic product serine-FDLA (HPS-FDLA) co-

injected with L-serine-FDLA

22

3

S1. 1H NMR of Compound 1 in DMSO-d6 at 400 MHz.

4

S2. 13

C NMR of Compound 1 in DMSO-d6 at 100 MHz.

5

S3. COSY of Compound 1 in DMSO-d6 at 400 MHz.

6

S4. HSQC of Compound 1 in DMSO-d6 at 400 MHz.

7

S5. HMBC of Compound 1 in DMSO-d6 at 400 MHz.

8

S6. ROESY of Compound 1 in DMSO-d6 at 400 MHz.

9

S7. 1H NMR of Compound 2 in CD3OD at 500 MHz.

10

S8. 13

C NMR of Compound 2 in CD3OD at 125 MHz.

11

S9. COSY of Compound 2 in DMSO-d6 at 500 MHz.

12

S10. ROESY of Compound 2 in DMSO-d6 at 500 MHz.

13

S11. HMBC of Compound 2 in DMSO-d6 at 500 MHz.

14

S12. HSQC of Compound 3 in DMSO-d6 at 500 MHz.

15

S13. 1H NMR of Compound 3 in DMSO-d6 at 500 MHz.

16

S14. 13

C NMR of Compound 3 in DMSO-d6 at 125 MHz.

17

S15. COSY of Compound 3 in DMSO-d6 at 500 MHz.

18

S16. HMBC of Compound 3 in DMSO-d6 at 500 MHz.

19

S17. HSQC of Compound 3 in DMSO-d6 at 500 MHz.

20

S18. ROESY of Compound 3 in DMSO-d6 at 500 MHz.

21

S19. Relevant part of the HPLC chromatogram of hydrolytic product serine-FDLA (HPS-FDLA) co-injected with D-serine-FDLA.

22

S20. Relevant part of the HPLC chromatogram of hydrolytic product serine-FDLA (HPS-FDLA) co-injected with L-serine-FDLA.