SyntheticApplications
withCyclopentyl
methyl ether(CPME)
Ver. 2.0

─1─CONTE

1. Alkylation, Silylation

NTS● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●2. Reactions under Lewis acid Conditions● ● ● ●

6● ● ● ●9● ● ● ● ● ● ● ●10● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●17

3. Reactions under Bronsted acid Conditions
4. Reaction with Base or Organometals
5. Oxidation/Reduction

6. Reactions with Transition Metal Catalyst● ● ● ● ● ●19● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●22● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●23

7. Reaction With Lipase
8. Polymerisation

9. Extraction/Crystallization
10. Others

3● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●24● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ● ●25

─2─

1. Alkylation, Silylation
1-1

O-Methylation of Pyridinol

1-2

N-Alkylation under PTC

1-3

Regioselective Ethynylation

Yamaguchi, The 126th Annual Meeting of thePharmaceutical Society of Japan (2005)

1-4

Asymmetric alkylation

Ooi, Angew Chem. int. Ed., 2008, 47, 1

1-5

Asymmetric conjugate addition

Maruoka, Org. Lett. 2009, 11, 2023

1-6

Asymmetric conjugate addition

J.A.Ellman, JACS 2009, 131, 8754

Torisawa, Fine Chemical 2006, 35, 53ibid

─3─

1-7

Asymmetric conjugate addition

J.A.Ellman, Chem.Sci., 2012, 3, 121

1-8

Enantioselective one-pot synthesis

Maruoka, Org. Lett. 2009, 11, 2023

1-9

Selective O-Silylation

Kamimura, J. Org. Chem. 2010, 75, 3579

1-10 Enantioselective allylation

M.Kotora, Chem. J. 2010, 16, 9442

─4─

1-11 Phase-Transfer-Catalyzed Oleﬁn Isomerization/-Alkylation Maruoka, Adv. Synth Catal. 2010, 352 ,165

1-12 5-silylethynyl-1,3-dioxolan-4-one as a new prochiral template Maruoka, Chem. Commun., 2010, 46, 7593

1-13 Methylation

Maruoka, Tetrahedron, Lett, 2008, 49, 5461

1-14 Allylation

Ooi, Synlett 2009, 4, 658

MTBE

─5─

2. Reactions under Lewis acid Conditions
2-1

Beckmann Rearrangement of Indanones Torisawa, Bioorganic & Medical Chem. Lett. 2007, 17, 453

2-2 ［3+4］Annulation Reaction

Takeda., Org.Lett., 2004, 6, 2277

2-3

Selective glycosylation

Fukase, Tetrahedron: Asymmetry. 2005, 16, 441

2-4

Selective glycosylation

Itoh, Tetrahedron, 2008, 64, 92

2-5

Selective glycosylation

Ikeda, TetrahedronLett., 2007, 48, 7431

─6─

2-6

Hetero Diels-Alder Reaction

2-7

Sulﬁnyl ketimine

2-8

Selective glycosylation

Kobayashi, Tetrahedron Lett., 2005, 46, 1803.

J.A.Ellman, J.Org.Chem, 2010, 75, 6283

Komba, J.Appl. Glycosci, 2011, 58, 1

─7─

2-9

Fucosylation

Horito, Carbohydrate Research, 2011, 346, 2098

2-10 Glycosylation

Itoh, Tetrahedron Lett, 2005, 46, 3521

─8─

3. Reactions under Bronsted acid Conditions
3-1

Pinner reaction

3-2

Deprotedtion of Boc-group

3-3Amination

Torisawa, Synth.Commun., 2009, 39, 2008

ibidJ.A.Ellman, J.Org.Chem., 2009, 74, 2646

Torisawa, Synth.Commun., 2009, 39, 2008

3-4

Asymmetric Cyclization

G.C.Fu, Angew Chem. int. Ed., 2009, 48, 2225.

3-5

Conjugate addition

Roberto Balliani, Green Chem., 2011, 13, 2026

─9─4. Reaction with Base or Organometals
4-1

Claisen-Schmidt Condensation

Torisawa, Summer Symposium of the JapaneseSociety for Process Chemistry (2005)

4-2

Chirality Transfer Methylation

Kawabata, Chem. Commun. 2003, 162

4-3

Chirality Transfer cyclization

Krause, SYNLETT. 2007, 1970

4-4

Selective KSA Formation

4-5

Symmetric aza-Morita-Baylis-Hillman Reaction

4-6

Grignard Addition Reactions

Tanabe, J.Org.Chem., 2007, 72, 8142

─ 10 ─

Sasai, Tetrahedron: Asymmetry 2006, 17, 578
idem. JACS., 2005, 127, 3680

Torisawa, Summer Symposium of the JapaneseSociety for Process Chemistry (2005)

4-7

New Grignard Addition reactions

4-8

Vinylic addition via carbenoids

Sato, Tetrahedron, 2005, 61, 4409

4-9

Asymmetric Michael Addition

Matsuyama, The 87th Spring Meeting ofChemical Society of Japan (2007)

4-10 Three Componet Coupling

Torisawa, Summer Symposium of the JapaneseSociety for Process Chemistry (2005)

Sato, Tetrahedron Lett., 2008, 49, 5073.

─ 11 ─

4-11 Three Componet Coupling

Sato, Chem. Lett., 2009, 38, 594.

4-12 Grignard Coupling

Ohshima, Synthesis, 2008, 2659.

4-13 Grignard Addition

Novartis Pharmaceuticals Corp., J. Org. Chem., 2008,73, 9016

─ 12 ─

4-14 Cross-coupling with diethylzinc

4-15 Intramolecular Robinson annulation

─ 13 ─

Ohshima, Tetrahedron, 2009,65, 1553.

Yamamoto, Chem. Commun.,2009,5412

4-16 Asymmetric Catalytic Cycloetheriﬁcation

4-17 Cross-coupling with Grignard reagent

Matsubara, JACS,2011,

Asami, Chem. Lett. 2011, 40, 983

4-18 Functionalisation of heteroarmatic N-oxides Kondo, Org. Biomol. Chem., 2011, 9, 78

4-19 Phosphinylation

Fujita, Tetrahedron: Asymmetry, 2010, 21, 711

─ 14 ─

4-20 Enantioselective Protonation

Shibata, Angew. Chem. Int. Ed, 2011, 50, 2249

4-21 Grignard coupling Shimada, The 2nd International Symosium on Process Chemistry(2011)4-22 Rearrangement

Nagase, Tetrahebron, 2011, 67, 6682

─ 15 ─

4-23 Protonation

Kobayashi, JACS,2010, 132, 7890

4-24 GrignardZeon Corporation, Internal data

4-25 Addition of Grignard reagent to CN-groupZeon Corporation, Internal data─ 16 ─5. Oxidation/Reduction
5-1

LiBH4 Reduction

Zeon Corporation, Cyclopentyl Methyl Ether (CPME) technical data

5-2

LiAlH4 Reduction

Maruoka, Angew Chem. int. Ed., 2003, 42, 5868

5-3

LiAlH4 Reduction

Shimada, J. Org Chem.,2005, 70, 10178.

5-4

i-Bu2AIH(DIBAL-H) Reduction Boehringer-Ingelheim Pharma., J. Org Chem. 2008, 73, 1524

5-5

MnO2 Oxidation

Zeon Corporation, Cyclopentyl Methyl Ether (CPME) technical data─ 17 ─5-6

Decomposition of azo-group

5-6

One pot process via radical reaction─ 18 ─Maruoka, Nature Chemistry, 2011, 3, 642

Kobayashi, The 2nd International
Symposium on Process Chemistry (2011)

6. Reactions with Transition Metal Catalyst
6-1

Ir-catalyzed Multi Component Coupling

6-2

Pd-catalyzed Transformation Mase, Org.Lett.,2004, 6, 458 G.A.Molander. J. Org. Chem.,2006, 71, 9198

Ishii, Chem. Commun.,2004, 6, 4587

G.A.Molander. Org. Lett.2007, 9, 1597

G.A.Molander. J. Org. Chem.,2008, 73, 2052.

G.A.Molander. J. Org. Chem.,2008, 73, 7481

6-3

Asymmetric Allyl Coupling

Fujita, J. Org. Chem. 2004, 69, 6679─ 19 ─

6-4

Buchwald-Hartwig Amination

6-5

Pd-catalyzed direct C-H arylation

H.Doucet, Chem Sus Chem, 2011, 4,16-6

Pd-catalyzed Cross-Coupling

G.A.Molander, J.ACS, 2010, 132,17108

6-7

Pd-catalyzed Cross-Coupling

G.A.Molander, Org. Lett.,2010, 12, 4876

─ 20 ─Sajiki, Gifu Yakkadaigaku Kiyou, 2006, 55, 45.

6-8

Pd-catalyzed oxidative functionalization

6-9

Ru-catalyzed Suzuki-Miyaura Coupling

Kuwano, The 57th Annual Meeting oforganometallic chemistry of Japan,2010

Itoh, Chem. Lett.,2010, 39,1050

6-10 Asymmetric Hosomi-Sakurai Reactions Kobayashi, Angew. Chem. Int. Ed., 2011, 50, 11121

6-11 Pd-catalyzed Negishi Coupling─ 21 ─

Tamao, Chem. Asian J.,2011, 6, 350

7. Reaction With Lipase
7-1

Selective Acylation

Fukunaga, Biotechnology Letters, 2005, 27, 383

7-2

Selective Acylation

Akai, Heterocycles, 2008, 76, 1537

─ 22 ─

8. Polymerisation
8-1

Cross Coupling

8-2

π―Conjugated polymers

Yamamoto, Polymer Journal, 2003, 35, 7, 603

Tomita, ACS National Meeting, 2011─ 23 ─9. Extraction/Crystallization
9-1

Crystallization

Shibasaki, Angew. Chem. Int. Ed., 2009, 48, 1070

9-2Crystallization

Oshiki, Syokubai, 2008, 50, 133

9-3

Removal of unreacted raw meterials

─ 24 ─Hotta, Organic Electronics, 2011, 12, 8

10. Others
10-1 Gold-nanoparticle

Mori, Chem. Commun., 2008, 3882

10-2 Hard formation of Peroxide

─ 25 ─

Sakakibara, Chem. Lett., 37,774 (2008)

10-3 Toxicological Data

10-4 Solvent selection guide

Merck, & Co., INC, Org. Process Res. Dev., 2011, 15, 939

Glaxo Smith Kline plc., Green. Chem. 2011, 13, 854

─ 26 ─

The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind
are made as to its accuracy, suitability for particular applications or results to be obtained.
Please read the Safety Data Sheet (SDS) carefully prior to handling.
This product was developed for the application in this brochure. In case of other applications, please handle under yourconfirmation of safety for the applications, or please talk to Zeon Corporation beforehand.

─ 27 ─

Specialty Chemicals Division

1-6-2 Marunouchi, Chiyoda-ku, Tokyo 100-8246 Japan
Phone:+81-3-3216-0542 Fax:+81-3-3216-1303
http://www.zeon.co.jp

Sep. 20180918005(SE)Printed in Japan─ 28 ─

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