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1 An Enantioselective Strategy for the Total Synthesis of (S)- Tylophorine via Catalytic Asymmetric Allylation and One-Pot DMAP-Promoted Isocyanate Formation/Lewis Acid Catalyzed Cyclization Sequence Bo Su, Hui Zhang, Meng Deng, and Qingmin Wang* State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s Republic of China [email protected]; [email protected] Table of contents 1. NMR spectra S2 2. HPLC data S13 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014

Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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Page 1: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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An Enantioselective Strategy for the Total Synthesis of (S)-Tylophorine via Catalytic Asymmetric Allylation and One-Pot DMAP-Promoted Isocyanate Formation/Lewis Acid Catalyzed Cyclization Sequence

Bo Su, Hui Zhang, Meng Deng, and Qingmin Wang*

State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s Republic of China

[email protected]; [email protected]

Table of contents1. NMR spectra S22. HPLC data S13

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014

Page 2: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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NMR Data

Page 3: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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Page 8: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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Page 12: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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Page 13: Tylophorine via Catalytic Asymmetric Allylation and One ... · 1 Det.ACh1 / 254m Detector A Chl 254mn Peak# Ret. Time 12.062 15.385 Tota 491391 375272 866663 49.947 50.053 100.000

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HPLC data

Conditions for racemic and enantiopure compound 3: Phenomenex Lux Cellulose-1 column, i-PrOH:Hexane = 30:70, 1.0 mL/min, 254nm。

HPLC data for recemic compound 3

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HPLC data for compound (R)-3

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Conditions for racemic and enantiopure tylophorine: Chiral AD-H column i-PrOH:Hexane = 30:70 (0.1% Et3N), 1.0 mL/min, 254nm。

HPLC data for racemic tylophorine

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HPLC data for (S)-tylophorine