total synthesis of tetraketide and cryptorigidifoliol i ... · pdf filer e tz aly ion...

56
Total Synthesis of Tetraketide and Cryptorigidifoliol I via a Sequential Allylation Strategy Birakishore Padhi, †,‡ G. Sudhakar Reddy, †,‡ and Debendra K. Mohapatra* ,†,‡ Natural Products Chemistry Division, CSIR-Indian Institute of Chemical Technology Hyderabad 500 007, India Academy of Scientific and Innovative Research, New Delhi, 110025, India [email protected] * Corresponding author. Tel.: +91-40-27193128; fax: +91-40-27160512 O O O 14 OH O O O Au Mg Au Ti Ti Reetz allylation Diastereoselective allylation Mitsunobu lactonization Mitsunobu lactonization Reetz allylation Diastereoselective allylation Maruoka allylation Sakurai allylation Tetraketide (1) Cryptorigidifoliol I (2)

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Page 1: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

Total Synthesis of Tetraketide and Cryptorigidifoliol I

via a Sequential Allylation Strategy

Birakishore Padhi,†,‡ G. Sudhakar Reddy,†,‡ and Debendra K. Mohapatra*,†,‡

†Natural Products Chemistry Division, CSIR-Indian Institute of Chemical Technology

Hyderabad 500 007, India

‡Academy of Scientific and Innovative Research, New Delhi, 110025, India

[email protected]

* Corresponding author. Tel.: +91-40-27193128; fax: +91-40-27160512

OO

O

14

OH OO

O

Au

Mg

Au

Ti

TiReetz allylation

Diastereoselective allylation

Mitsunobu lactonization

Mitsunobu lactonization Reetz allylation

Diastereoselective allylation

Maruoka allylation

Sakurai allylation

Tetraketide (1) Cryptorigidifoliol I (2)

Page 2: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S2

Table of Contents

Ser. No. Description Page No.

1 1H and 13C NMR Copy of 20 S4 S5

2 1H and 13C NMR Copy of 21 S6 S7

3 HPLC of Chromatogram of 21 S8 S9

4 1H and 13C NMR Copy of 22 S10 S11

5 1H and 13C NMR Copy of 23 S12 S13

6 1H and 13C NMR Copy of 13 S14 S15

7 1H and 13C NMR Copy of 24 S16 S17

8 1H and 13C NMR Copy of 12 S18 S19

9 1H and 13C NMR Copy of 1 S20 S21

9 1H and 13C NMR Copy of 18 S22 S23

10 1H and 13C NMR Copy of 28 S24 S25

11 1H and 13C NMR Copy of 29 S26 S27

12 HPLC Chromatogram of 29 S28 S29

13 1H and 13C NMR Copy of 31 S30 S31

14 1H and 13C NMR Copy of 32 S32 S33

1H and 13C NMR Copy of 32 S34 S35

16 HPLC Chromatogram of 33 S36 S37

17 1H and 13C NMR Copy of 34 S38 S39

18 1H and 13C NMR Copy of 35 S40 S41

19 1H and 13C NMR Copy of 36 S42 S43

20 1H and 13C NMR Copy of 17 S44 S45

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S3

21 1H and 13C NMR Copy of 37 S46 S47

22 HPLC Chromatogram of 37 S48 S49

23 1H and 13C NMR Copy of 16 S50 S51

24 1H and 13C NMR Copy of 15 S52 S53

25 1H and 13C NMR Copy of 2 S54 S55

26 HRMS (ESI) copy of 2 S56

Page 4: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S4

1H NMR Spectrum of 20 (500 MHz, CDCl3)

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S5

13C NMR Spectrum of 20 (100 MHz, CDCl3)

Page 6: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S6

1H NMR Spectrum of 21 (400 MHz, CDCl3)

Page 7: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S7

13C NMR Spectrum of 21 (125 MHz, CDCl3)

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S8

HPLC Chromatogram of 21

OHOBn

Page 9: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S9

LC-MS Chromatogram of 21

Page 10: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S10

1H NMR Spectrum of 22 (500 MHz, CDCl3)

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S11

13C NMR Spectrum of 22 (75 MHz, CDCl3)

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S12

1H NMR Spectrum of 23 (500 MHz, CDCl3)

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S13

13C NMR Spectrum of 23 (125 MHz, CDCl3)

Page 14: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S14

1H NMR Spectrum of 13 (400 MHz, CDCl3)

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S15

13C NMR Spectrum of 13 (125 MHz, CDCl3)

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S16

1H NMR Spectrum of 24 (300 MHz, CDCl3)

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13C NMR Spectrum of 24 (75 MHz, CDCl3)

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S18

1H NMR Spectrum of 12 (500 MHz, CDCl3)

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S19

13C NMR Spectrum of 12 (125 MHz, CDCl3)

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S20

1H NMR Spectrum of 1 (300 MHz, CDCl3:C6D6 = 1:1)

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13C of NMR Spectrum 1 (100 MHz, CDCl3:C6D6 = 1:1)

Page 22: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S22

1H NMR Spectrum of 18 (300 MHz, CDCl3)

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S23

13C NMR Spectrum of 18 (100 MHz, CDCl3)

Page 24: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S24

1H NMR Spectrum of 28 (500 MHz, CDCl3)

Page 25: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S25

13C NMR Spectrum of 28 (125 MHz, CDCl3)

Page 26: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S26

1H NMR Spectrum of 29 (400 MHz, CDCl3)

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P a g e | 27

S27

13C NMR Spectrum of 29 (100 MHz, CDCl3)

Page 28: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S28

HPLC Chromatogram of 29

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S29

LC-MS Chromatogram of 29

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S30

1H NMR Spectrum of 31 (400 MHz, CDCl3)

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S31

13C NMR Spectrum of 31 (100 MHz, CDCl3)

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S32

1H NMR Spectrum of 32 (400 MHz, CDCl3)

Page 33: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S33

13C NMR Spectrum of 32 (125 MHz, CDCl3)

Page 34: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S34

1H NMR Spectrum of 33 (400 MHz, CDCl3)

Page 35: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S35

13C NMR Spectrum of 33 (125 MHz, CDCl3)

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S36

HPLC Chromatogram of 33

Page 37: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S37

LC-MS Chromatogram of 33

Page 38: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

P a g e | 38

S38

1H NMR Spectrum of 34 (400 MHz, CDCl3)

Page 39: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

P a g e | 39

S39

13C NMR Spectrum of 34 (125 MHz, CDCl3)

Page 40: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S40

1H NMR Spectrum of 35 (500 MHz, CDCl3)

Page 41: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S41

13C NMR Spectrum of 35 (75 MHz, CDCl3)

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S42

1H NMR Spectrum of 36 (400 MHz, CDCl3)

Page 43: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S43

13C NMR Spectrum of 36 (75 MHz, CDCl3)

Page 44: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S44

1H NMR Spectrum of 17 (400 MHz, CDCl3)

Page 45: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S45

13C of 17 (75 MHz, CDCl3)

Page 46: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S46

1H NMR Spectrum of 37 (400 MHz, CDCl3)

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S47

13C NMR Spectrum of 37 (75 MHz, CDCl3)

Page 48: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S48

HPLC Chromatogram of 37

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S49

LC-MS Chromatogram of 37

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S50

1H NMR Spectrum of 16 (400 MHz, CDCl3)

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S51

13C NMR Spectrum of 16 (100 MHz, CDCl3)

Page 52: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S52

1H NMR Spectrum of 15 (500 MHz, CDCl3)

Page 53: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S53

13C NMR Spectrum of 15 (125 MHz, CDCl3)

Page 54: Total Synthesis of Tetraketide and Cryptorigidifoliol I ... · PDF fileR e tz aly ion Diastereoselective allylation ... P a g e | 3 S3 21 1H and 13C ... S47 22 HPLC Chromatogram of

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S54

1H NMR Spectrum of 2 (500 MHz, CDCl3)

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S55

13C NMR Spectrum of 2 (125 MHz, CDCl3)

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HRMS(ESI) Chromatogram of 2