Cationic cyclization cascades - uni-konstanz.de

Cationic cyclizationcascadesKonstantin Samarin

Gaich-Group Seminar28.10.2013

Stork-Eschenmoser Hypothesis

2

Gaich-Group SeminarKonstantin Samarin

Stork G., Burgstrahler A.W. J. Am. Chem. Soc. 1955, 77, 5068-5077Eschenmoser A., Ruzicka L., Jeger O., Arigoni D. Helv. Chim. Acta. 1955, 38, 1890-1904

Synthesis of 11α-hydroxyprogesterone

3


Johnson W.S., Brinkmeyer R.S., Kapoor V.M., Yarnell T.M. J. Am. Chem. Soc. 1977, 99, 8341-8343

HO

H

HO

pro-C-11

a) TFA, CF3CH2OH0 oC

35%

H

HO

O

b) Ac2O, pyrc) O3 ; Zn, AcOHd) KOH

H

HO

O

O

11 - hydroxyprogesterone

80%, dr 92:8

7 8

9

Synthesis of d-4β-hydroxyandrostan-17-one

4


Johnson W.S., Fletcher V.R., Chenera V.R., Bartlett W.R., Tham F.S., Kullning R.K. J. Am. Chem. Soc. 1993, 115, 497-504

Synthesis of (±)-Sophoradiol

5


Fish P.V., Johnson W.S. J. Org. Chem. 1994, 59, 2324-2335

Yamamoto’s Enantioselective Olefin Protonation-Initiated Polycyclization

6


Ishihara K., Nakamura S., Yamamoto H. J. Am. Chem. Soc. 1999, 121, 4906-4907Ishihara K., Ishibashi H., Yamamoto H. J. Am. Chem. Soc. 2002, 124, 3647-3655

Yamamoto’s Enantioselective Olefin Protonation-Initiated Polycyclization

7


Ishihara K., Ishibashi H., Yamamoto H. J. Am. Chem. Soc. 2002, 124, 3647-3655

OTBDPSa) 200 mol% (R) - 2toluene, -78 C, 3 days

b) TBAF

OH OH

78% ee11 : 89

c) Ac2Od) BF3 Et2O, CH3NO2, rt

H

OAc

89%, 75% eeH

O

2324 25

2627

Total Synthesis of Dammarenediol

8


Corey E. J., Lin S. J. Am. Chem. Soc. 1996, 118, 8765-8766

Total Synthesis of Hexacyclic Sedimentary Triterpene

9


Corey E. J., Luo G.,Lin L. S. Angew. Chem. Int. Ed. 1998, 37, 1126-1128

Nazarov-trigered polycyclization

10


Bender J.A., Arif A.M., West F.G. J. Am. Chem. Soc. 1999, 121, 7443-7444

Nazarov–[4 + 3]-cycloaddition

11


Wang Y., Schill B.D., Arif A.M., West F.G. Org. Lett. 2003, 5, 2747-2750Yungai A, West F.G. Tetrahedron Lett. 2004, 45, 5445-5448

The halocyclopropane Nazarov reaction

12


Grant N.T. PhD thesis, University of Alberta, Edmonton, AB, 2008.

Non-traditional interrupted Nazarov reactions

13


Grant T.N., West F.G. Org. Lett. 2007, 9, 3789-3792

TIPSO ClCl

AgBF4MeCN, reflux

80%

O

TIPSO ClCl

Br AgBF4MeCN, reflux

48%

O

Br

TIPSO ClCl

AgBF4MeCN, reflux

48%

OMeO

MeO

Cl

5253

5455

56 57

Platinum-Catalyzed EnantioselectivePolycyclization Reactions

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Mullen C.A., Campbell A.N., Gagne M.R. Angew. Chem. Int. Ed.2008, 47, 6011-6014

HO

P2Pt2+

Ph3COMe

Ph3C

MeOH

O

HPtP

PO

H

PtHP

P

Ph3C

Ph3CH

P

P

(S)-xylyl-phanephos

58

59

6061

15


Mullen C.A., Campbell A.N., Gagne M.R. Angew. Chem. Int. Ed.2008, 47, 6011-6014

Platinum-Catalyzed Enantioselective Polycyclization Reactions

Gold(I)-Catalyzed EnantioselectivePolycyclization Reactions

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Sethofer S.G., Mayer T., Toste F.D. J. Am. Chem. Soc. 2010, 133, 8276-8277

Indium(III)-Catalyzed Cationic Cascade

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Surendra K., Qiu W.W., Corey E.J. J. Am. Chem. Soc. 2011, 133, 9724-9726

Enantioselective Proton-Initiated Polycyclization of Polyenes

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Surendra K., Corey E.J. J. Am. Chem. Soc. 2012, 134, 11992-11994

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Surendra K., Corey E.J. J. Am. Chem. Soc. 2012, 134, 11992-11994

Enantioselective Proton-Initiated Polycyclization of Polyenes

α-Keto-Esters as Initiators of Cationic Polycyclization

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Zhao Y.-J., Li B., Tan L.-J. S., Shen Z.-L., Loh T.-P. J. Am. Chem. Soc. 2010, 132, 10242-10244

Thiourea-Catalyzed Cationic Polycyclization

21


Knowles R.R., Lin S., Jacobsen E.N. J. Am. Chem. Soc. 2010, 132, 5030-5032

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Knowles R.R., Lin S., Jacobsen E.N. J. Am. Chem. Soc. 2010, 132, 5030-5032

Thiourea-Catalyzed Cationic Polycyclization

Ishihara’s halocyclization method

23


Sakakura A., Ukai A., Ishihara K. Nature. 2007, 445, 900-903

24




25




Phosphite-urea catalysts for bromocyclization

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Sawamura Y., Nakatsuji H., Sakakura A., Ishihara K. Chem. Sci. 2013, 4, 4181-4186

NBr

O

O

ArOP

ArOArO

step 1

ArOP

ArOArO

Br

N

O

O

N

O

O

ArOP

ArOArO Br

step 2

Br

BrBr

BrH

Cyclization

N

O

O

ArHOP

ArOArO N

O

O

BrH

1 : 2in each reaction

143 155

156

157158

159 160

161

162

163


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O

NH

NH

OAr'

PArO

ArO

NBr

O

O

O

NH

NH

OAr'

PArO

ArOBr

NO

O

O

NH

NH

OAr'

PArO

ArOO

N

O

Br

156164

165 166


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Barluenga’s Hypervalent IodoniumReagent

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Barluenga J., Trincado M., Rubio E., Gonzalez J. J. Am. Chem. Soc. 2004, 126, 3416-3417

Barluenga’s Hypervalent IodoniumReagent

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Barluenga J., Trincado M., Rubio E., Gonzalez J. J. Am. Chem. Soc. 2004, 126, 3416-3417

Snyder’s reagents for halocyclizations

31


Snyder S.A., Treitler D.S., Brucks A.P. J. Am. Chem. Soc. 2010, 132, 14303-14314


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33




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OMe

IDSI (1.2 equiv.),CH3NO2, -25 C, 5 min

OMe

IH

90%

Br

IH

85%

MOMO

OMOM

Br

OMOM

a) IDSI (1.2 equiv.),CH3NO2, -25 C, 30 min

IH58%

b) Me3SO3H (15 equiv.)1h

186 195

188 196

190197

H

IDSI (1.2 equiv.),CH3NO2, -25 C, 5 min

2:1


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OHOIDSI (1.2 equiv),CH3NO2, 5 min, -25 C

79%, 19:1 dr

OO

HI

LiCl, DMF80 C, 12h

OO

H

OO

loliolide

198 199

200201

97%


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Non-stop tail-to-head polycyclization

37


Pronin S.V., Shenvi R.A. Nat. Chem. 2012, 4, 915-920

Non-stop tail-to-head polycyclization

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Pronin S.V., Shenvi R.A. Nat. Chem. 2012, 4, 915-920

Thank you for attention!

Questions?

39

Cationic cyclization cascades - uni-konstanz.de

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