General Papers

ARKIVOC 2015 (vii) S1-S13

Supplementary Material

Total synthesis of amorfrutin B via a Pd-catalyzed regioselective geranyl migration-decarboxylation-cycloaromatization cascade Chao Wang,*a Yajun Kong,a and Hongyun Qiao b a

b

School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, P. R. China Research & Development Department, ChemPartner Inc., Zhangjiang Hi-Tech Park, Shanghai 201 203, China E-mail: [email protected]

Table of Contents

1. NMR and assignment of compound 3 2. NMR and assignment of compound 6 3. NMR and assignment of compound 9 4. NMR and assignment of compound 10 5. NMR and assignment of compound 13 6. NMR and assignment of Amorfrutin B

S2 S4 S6 S8 S10 S12

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General Papers

ARKIVOC 2015 (vii) S1-S13

Compound 3

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ARKIVOC 2015 (vii) S1-S13

1

δ /ppm 8.60 (brs, 1H) 5.35 (t, J = 7.3 Hz, 1H) 5.08 (t, J = 6.1 Hz, 1H) 4.70 (d, J = 7.2 Hz, 2H) 3.44 (s, 2H) 2.13 - 2.05 (m, 4H) 1.71 (s, 3H) 1.68 (s, 3H), 1.60 (s, 3H)

H Assignment

COOH CH2CH3C=CH (CH3)2C=CH OCH2 COCH2CO C=CHCH2CH2CH=CH CH=CCH3 C=CCH3CH3

13

δ /ppm

C Assignment

171.5 166.9 143.4, 131.8, 122.2, 117.4 62.8 40.8 39.5, 26.2 25.6, 17.6, 16.5

COOH COOR (CH3)2C=CH, (CH3)RC=CH OCH2 CO-CH2-CO C=CCH2CH2C=C C=CC(CH3)2,C=CCH3R

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Compound 6

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1

δ/ppm 5.36 (s, 1H) 5.35 (mc, 1H) 5.06 (mc, 1H) 4.67, 4.66 (d, 2H, J = 7.2 Hz) 3.51 (s, 2H) 3.50 (s, 2H) 2.10 - 2.05 (m, 4H) 1.70 (s, 9H) 1.67 (s, 3H), 1.59 (s, 3H)

H Assignment

CH3C=CH (CH3)2C=CH OC=CHCOO OCH2 COCH2CO COCH2C=CH C=CHCH2CH2 O2C(CH3)2, C=CCH3 C=C(CH3)2

13

δ /ppm

C Assignment

195.7 166.4 163.6 160.5 143.6, 123.5 131.9,117.3 107.3 97.1 62.6 49.1, 46.9 39.5, 32.2 26.2, 25.7, 24.9, 17.7, 16.5

CH2COCH2 COCH2COOR CHCOOC(CH3)2 COCH2CO CH=CCH3R CH=C(CH3)2 O2C(CH3)2 OC=CHCOO OCH2 COCH2CO, C=CCH2CO C=CCH2CH2C=C OC(CH3)2, C=C(CH3)2, C=CCH3R

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Compound 9

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δ/ppm 7.28, 7.27, 7.20, 7.19 (m, 5H) 5.38 (m, 1H) 5.35 (s, 1H) 5.28 (s,1H) 5.05 (mc, 1H) 4.73 (d, 2H, J = 7.4 Hz) 3.69 (s, 2H) 3.04 - 2.95 (m, 4H) 2.07 - 2.05 (m, 4H) 1.71 -1.59 (s, 15H)

H Assignment Ar-H

CH3C=CH (CH3)2C=CH COCCOO OC=CHCOO OCH2CH=C COCH2CO COCH2CH2Ar C=CHCH2CH2C=C O2C(CH3)2, C=CCH3 C=C(CH3)2

，

13

δ /ppm

C Assignment

197.5 192.5 165.2 165.1 160.8 140.3 129.0, 117.4 128.5, 128.3, 128.2 123.5, 108.7 107.2 96.5 62.0 61.8 42.7 39.5, 31.7 39.3, 32.2 26.2, 25.7, 24.9, 17.7, 16.5

CH2C=OCHCOCH2CH2Ar ArCH2CH2C=O COOCH2=CRCH3 CHCOOC(CH3)2 CH=CO Ar(C)CH2CH2 CH=C(CH3)R Ar(C) CH=C(CH3)2 O2C(CH3)2 OC=CHCOO COCH2COO OCH2CH C=CCH2CO C=CCH2CH2C=C ArCH2CH2 OC(CH3)2, C=C(CH3)2, C=CCH3R

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Compound 10

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1

δ/ppm 7.31 - 7.23 (m, 5H) 6.40 (s, 1H) 5.21 (t, 1H, J = 7.2 Hz) 5.06 (t, 1H, J = 7.2 Hz) 3.34, 3.33 (d, 2H, J = 7.3 Hz ) 2.98 - 2.88 (m, 4H) 2.10 - 2.05 (m, 4H) 1.80, 1.69, 1.68, 1.60 (s, 15H)

H Assignment

Ar-H Ar-H RCH3C=CH (CH3)2C=CH ArCH2CH=C ArCH2CH2Ar C=CHCH2CH2C=C O2C(CH3)2, C=CCH3, C=C(CH3)2,

13

δ /ppm

C Assignment

160.2 156.2 152.4 146.3, 125.8 141.9, 140.2 132.1,126.4 128.7, 128.6, 128.3 122.8 120.8 113.2 104.7 39.7, 30.7 37.5, 36.7 26.4, 17.7 25.7 22.7, 21.9, 16.2

Ar-COOR Ar(C)-OH Ar(C)-OC(CH3)2 CH=C(CH3)R Ar(C)-CH2CH2-Ar(C) CH=C(CH3)2 Ar Ar(C)-CH2C=C Ar(C)-COOR OC(CH3)2 Ar(C) C=CCH2CH2C=C ArCH2CH2Ar C=C(CH3)2 Ar-CH2-C=C C(CH3)2, C=CCH3R

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Compound 13

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1

δ/ppm 7.23, 7.19, 7.15 (m, 5H) 6.32 (s,1H) 5.12 (t, 1H, J = 7.2 Hz) 4.98 (t, 1H, J = 7.2 Hz) 3.78 (s, 3H) 3.27, 3.25 (d, 2H, J = 7.3 Hz) 2.90 - 2.80 (m, 4H) 2.02 - 1.97 (m, 4H) 1.72, 1.60, 1.52 (s, 15H)

H Assignment

Ar-H Ar-H RCH3C=CH (CH3)2C=CH COCH3 ArCH2CH=C ArCH2CH2Ar C=CHCH2CH2C=C O2C(CH3)2, C=CCH3, C=C(CH3)2,

13

δ /ppm

C Assignment

160.3 156.3 152.4 146.5,126.5 141.9, 140.3 132.1,125.9 128.8, 128.7, 128.4 122.9 120.8 113.3 104.7 56.4 39.8, 30.9 37.4, 36.9 26.5,17.8 25.7 22.9, 22.1, 16.3

Ar-COOR Ar(C)-OH Ar(C)-OC(CH3)2 CH=C(CH3)R Ar(C)-CH2CH2-Ar(C) CH=C(CH3)2 Ar Ar(C)-CH2C=C Ar(C)-COOR OC(CH3)2 Ar(C) OCH3 C=CCH2CH2C=C ArCH2CH2Ar C=C(CH3)2 Ar-CH2-C=C C(CH3)2, C=CCH3R

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Amorfrutin B

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1

δ/ppm 7.21 - 7.13 (m, 5H) 6.29 (s, 1H) 5.16 (t, 1H, J = 7.1 Hz) 4.98 (t, 1H, J = 7.1 Hz) 3.69 (s, 3H) 3.32, 3.31 (d, 2H, J = 7.3 Hz) 2.81- 2.77 (m, 4H) 2.01 - 1.96 (m, 4H) 1.72 (s, 3H ), 1.60 (s, 3H ), 1.51 (s, 3H )

H Assignment

Ar-H OH RCH3C=CH (CH3)2C=CH OCH3 ArCH2CH=C ArCH2CH2Ar C=CHCH2CH2C=C C=CCH3, C=CCH3CH3

13

δ /ppm

C Assignment

157.7 155.5 141.8 141.3 137.9 131.8, 123.9 128.5, 128.3 125.9, 122.1 112.7 108.9 103.6 55.7 39.7, 26.5 38.0, 37.7 25.7,17.7 22.1 16.1

COOH Ar(C)-OCH3 Ar(C)-OH Ar(C)-CH2CH2 CH2CH2-Ar(C) CH=C(CH3)R Ar CH=C(CH3)2 Ar(C)-CH2C=C Ar(C)-COOH Ar(C) OCH3 C=CCH2CH2C=C ArCH2CH2Ar C=C(CH3)2 Ar-CH2-C=C C=CCH3R

S13

Supplementary Material - Arkivoc

General Papers. ARKIVOC 2015 (vii) S1-S13. Page S3. ©ARKAT-USA, Inc. δ /ppm. 1. H Assignment. 8.60 (brs, 1H). 5.35 (t, J = 7.3 Hz, 1H). 5.08 (t, J = 6.1 Hz, ...
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