Top Banner
Terpene Cyclization inside supramolecular capsule catalyst 2017 8/26 M2 Kei Ito 1
44

Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Mar 16, 2020

Download

Documents

dariahiddleston
Welcome message from author
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Page 1: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Terpene Cyclization inside supramolecular capsule catalyst

2017 8/26

M2 Kei Ito

1

Page 2: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

1. Introduction

2. Today`s contents ~tail-to-head terpene (THT) cyclization in capsule catalyst~ 3. Summary

2

Page 3: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Terpenes, Terpenoids

IUPAC GOLD BOOK

3

Page 4: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Category of terpene, terpenoid

David W. Chem. Rev, 2006, 106, 3412-3442

4

Page 5: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Diversity of terpene, terpenoid

David W. Chem. Rev, 2006, 106, 3412-3442

Simple Mono-Terpene has structurally diversity

5

Page 6: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

HTT and THT cyclization

Surgey V. et. al, Nat. Chem, 2012, 4, 915

HTT (Head-to-Tail Terpene)

THT (Tail-to-Head Terpene)

・Reproducible in bulk solvent

・ Mainly yielding

decaline framework

・Lacking example in bulk solvent (Man-made catalyst)

・Produce a diverse variety

of frameworks

6

Page 7: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

HTT cyclization(1)

Stork-Eschenmoser`s hypothesis (1950`s)

G. Stork. et. al, J. Am. Chem. Soc, 1955, 77, 5068

A. Eschenmoser. et. al, ibid, 1955, 38, 1890

W. S. Johnson, Acc. Chem. Res, 1968, 1, 1

7

Page 8: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

HTT cyclization(2)

Biomimetic synthesis of steroids

William. S. Johnson. et. al, J. Am. Chem. Soc, 1977, 99, 8341

Corey. E. J. et. al, J. Am. Chem. Soc, 1996, 118, 8765

8

Page 9: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

HTT cyclization(3)

Enantioselective biomimetic cyclization

Yamamoto. H. et. al, J. Am. Chem. Soc, 2002, 124, 3647

Yamamoto. H. et. al, J. Am. Chem. Soc, 1999, 121, 4906

First example of enantioselective cyclization

9

Page 10: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Difficulty of THT cyclization(1)

D. D. Syrdal. et.al, Tetrahedron. Lett, 1972, 24, 2455

10

Page 11: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Difficulty of THT cyclization(2)

Hirose. Y. et.al, Chem. Lett, 1972, 263

Yamamoto. H. et.al, J. Am. Chem. Soc, 1983, 105, 6154

11

Page 12: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

What makes THT cyclization difficult?(1)

Norman. L. Allinger. et. al, J. Am. Chem. Soc, 1975, 97, 752

David W. Chem. Rev, 2006, 106, 3412-3442

12

Page 13: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

In bulk solvent

Stabilization of cationic intermediate is absent

Rudolf. K. Allemann, et. al, Bioorganic & Medicinal Chemistry, 2017, ASAP

Surgey V. et. al, Nat. Chem, 2012, 4, 915

13 What makes THT cyclization difficult?(2)

Page 14: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Joseph. P. Noel. et. al, Science, 1997, 277, 1815

14 What makes THT cyclization difficult?(3)

Page 15: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

1. Introduction

2. Today`s contents ~tail-to-head terpene (THT) cyclization in capsule catalyst~ 3. Summary

15

Page 16: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Today`s topic

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Konard Tiefenbacher

https://nanocat.chemie.unibas.ch/en/welcome/konrad/

University of Basel Department of chemistry ETH Zürich Department of Biosystems Science and Engineering

16

Page 17: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Supramolecular capsule

・Octahedral capsule (6* Resorcinarene +8*H2O )

・ Self-assembly by 60 H-bonds

intermolecular O-H・・・O

intramolecular O-H・・・O intramolecular (with H2O) O-H・・・O

Leonard. R. MacGillvray. et.al, Nature, 1997, 389, 469

{ K. Tiefenbacher et. al, Nat. chem, 2015, 7, 197

17

Page 18: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Capsule stabilizing cationic guest

Cation-π interaction stabilize cationic guest in cavity

Shivanyuk. A .et.al, Proc. Natl. Acad. Sci, 2001, 98, 7662

18

Page 19: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Merits of using capsule catalyst 19

Page 20: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Potential of capsule catalyst for THT(1)

Capsule works as a brønsted acid

Estimated pKa: 5.5~6.0 Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2013, 135, 16213

20

Page 21: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Potential of capsule catalyst for THT(2)

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2013, 135, 16213

Potential for activation of acyclic terpene by protonation

21

Page 22: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization(1)

K. Tiefenbacher et. al, Nat. chem, 2015, 7, 197

22

Page 23: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization(2)

K. Tiefenbacher et. al, Nat. chem, 2015, 7, 197

23

Page 24: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization(3)

K. Tiefenbacher et. al, Nat. chem, 2015, 7, 197

24

Page 25: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Reaction condition (Effect of acid)(1)

Different cyclization yield depending on supplier of CDCl3

NMR spectrum of catalyst in CDCl3 NMR spectrum of catalyst in CDCl3(treat with Al2O3)

Broadening of OH and H2O is observed with CDCl3 without stabilizer (Fast proton exchange)

Removal of DCl gives sharp peaks of OH and H2O

Trace DCl causes protonation of capsule

25

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 26: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Cyclization with different amount of DCl

0 mol% DCl No conversion

・Removal of capsule (3 mol% DCl) No conversion

Combination of capsule and acid is necessary for cyclization

26 Reaction condition (Effect of acid)(2)

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 27: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Reaction inside the capsule

Reaction inside the capsule

Reaction inside the capsule is necessary for cyclization

27

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 28: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Remarkable point of capsule catalyst

E.J. Leὰo Lana. et. al, J. Mol. Catal, 2006, 259, 99

Tristan. H. Lambert, et. al, Org. Lett, 2009, 11, 1381

28

Page 29: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Mechanism analysis (Eucalyptol)

1. Protonation step

rCS= recombinant 1,8-cineol synthase

Similar protonation to cyclase enzyme

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Rodney. Croteau, et. al, J. Am. Chem. Soc, 2002, 124, 8546

29

Page 30: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Mechanism analysis (Isotope-labeling)

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

30

Page 31: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization (other LGs)(1)

・H2O (leaving group) causes quenching of cationic intermediate

Other leaving group (weak nucleophilicity) shows other selectivity?

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

31

Page 32: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization (other LGs)(2)

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

32

Page 33: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Cyclization in SN1 or SN2 type manner(1) 33

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 34: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Cyclization in SN1 or SN2 type manner(2)

Proposed mechanism of different selectivity

34

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 35: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization (other LGs)(3) 35

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 36: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Results of THT cyclization (other LGs)(4) 36

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 37: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Affinity and reaction selectivity(1)

Encapsulation ratio of substrates with different LGs (Affinity)

Lower affinity Lower selectivity (SN2 (+ SN1))

Higher affinity

Higher selectivity (SN1)

37

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 38: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

38 Affinity and reaction selectivity(2)

Page 39: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Kinetic investigations(1)

1st order on capsuleⅠ 1st order consumption of SM

𝑣 =𝑘𝑜𝑏𝑠[GOAc][Ⅰ]

39

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 40: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Kinetic investigations(2)

Eyring equation

ln𝒌

𝑻 =-

∆𝑯≠

𝑹

𝟏

𝑻+

∆𝑺≠

𝑹+ln

𝒌𝑩

𝒉

∆𝐻≠= −(−13568) × 8.31/4.2 ≈27.0 (kcal・mol−1)

∆𝑆≠= (29.3 − 23.76) × 8.31/4.2 ≈ 11.0(cal・mol−1)

※ln𝒌𝑩

𝒉=23.76

∆𝑆≠> 0 ⇒ Disordered state = Rate determining step

Cleavage of LG

Rate determining step

=

40

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 41: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Kinetic investigations(3) 41

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 42: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Kinetic investigations(4)

≒ Steady-state

𝑘2[𝐒@𝐈𝐇+]=(𝑘−2+𝑘3) 𝐒𝐇+@𝐈

𝐾1 =[𝐒@𝐈𝐇+]

𝐈𝐇+ [𝐒]≈

[𝐒@𝐈𝐇+]

𝐈 [𝐒]

𝑣 = 𝑘3[𝐒𝐇+@𝐈]

=𝐾1𝑘2𝑘3

𝑘−2+𝑘3[ 𝐈 [𝐒]

Proposed mechanism for cyclization of GOAc

42

Konard. Tiefenbacher. et. al, J. Am. Chem. Soc, 2017, ASAP

Page 43: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

1. Introduction

2. Today`s contents ~tail-to-head terpene (THT) cyclization in capsule catalyst~ 3. Summary

43

Page 44: Terpene Cyclization inside capsule catalystkanai/seminar/pdf/Lit_K_Ito_M2.pdf · Diversity of terpene, terpenoid David W.Chem. Rev, 2006, 106, 3412-3442 Simple Mono-Terpene has structurally

Summary

・ Self assembly capsule can catalyze THT cyclization

・ Selectivity of the reaction is changed by

44