Enantioselective Dichlorination of Allylic Alcohols

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2011 May 6

PMID 21542622

Citations 41

Authors

K C Nicolaou

Nicholas L Simmons

Yongcheng Ying

Philipp M Heretsch

Jason S Chen

Affiliations

Soon will be listed here.

Abstract

The development of an enantioselective allylic alcohol dichlorination catalyzed by dimeric cinchona alkaloid derivatives and employing aryl iododichlorides as chlorine sources is reported. Reaction optimization, exploration of the substrate scope, and a model for stereoinduction are presented.

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References

Yoshimitsu T, Fukumoto N, Tanaka T . Enantiocontrolled synthesis of polychlorinated hydrocarbon motifs: a nucleophilic multiple chlorination process revisited. J Org Chem. 2008; 74(2):696-702. DOI: 10.1021/jo802093d. View

Yousefi R, Whitehead D, Mueller J, Staples R, Borhan B . On the chlorenium source in the asymmetric chlorolactonization reaction. Org Lett. 2011; 13(4):608-11. DOI: 10.1021/ol102850m. View

Snyder S, Treitler D, Brucks A . Simple reagents for direct halonium-induced polyene cyclizations. J Am Chem Soc. 2010; 132(40):14303-14. DOI: 10.1021/ja106813s. View

Mooney C, Haines T . Chlorination and sulfation reactions in the biosynthesis of chlorosulfolipids in Ochromonas danica, in vivo. Biochemistry. 1973; 12(22):4469-72. DOI: 10.1021/bi00746a026. View

Yoshimitsu T, Nakatani R, Kobayashi A, Tanaka T . Asymmetric total synthesis of (+)-danicalipin A. Org Lett. 2011; 13(5):908-11. DOI: 10.1021/ol1029518. View

Denmark S, Burk M, Hoover A . On the absolute configurational stability of bromonium and chloronium ions. J Am Chem Soc. 2010; 132(4):1232-3. DOI: 10.1021/ja909965h. View

ELOVSON J, VAGELOS P . A new class of lipids: chlorosulfolipids. Proc Natl Acad Sci U S A. 1969; 62(3):957-63. PMC: 223692. DOI: 10.1073/pnas.62.3.957. View

Bedke D, Shibuya G, Pereira A, Gerwick W, Haines T, Vanderwal C . Relative stereochemistry determination and synthesis of the major chlorosulfolipid from Ochromonas danica. J Am Chem Soc. 2009; 131(22):7570-2. DOI: 10.1021/ja902138w. View

Bedke D, Shibuya G, Pereira A, Gerwick W, Vanderwal C . A concise enantioselective synthesis of the chlorosulfolipid malhamensilipin A. J Am Chem Soc. 2010; 132(8):2542-3. PMC: 2830791. DOI: 10.1021/ja910809c. View

10.

Nilewski C, Geisser R, Carreira E . Total synthesis of a chlorosulpholipid cytotoxin associated with seafood poisoning. Nature. 2009; 457(7229):573-6. DOI: 10.1038/nature07734. View

11.

Brochu M, Brown S, MacMillan D . Direct and enantioselective organocatalytic alpha-chlorination of aldehydes. J Am Chem Soc. 2004; 126(13):4108-9. DOI: 10.1021/ja049562z. View

12.

ELOVSON J, VAGELOS P . Structure of the major species of chlorosulfolipid from Ochromonas danica. 2,2,11,13,15,16-hexachloro-N-docosane 1,14-disulfate. Biochemistry. 1970; 9(16):3110-26. DOI: 10.1021/bi00818a002. View

13.

Ciminiello P, DellAversano C, Fattorusso E, Forino M, Magno S, Di Rosa M . Structure and stereochemistry of a new cytotoxic polychlorinated sulfolipid from Adriatic shellfish. J Am Chem Soc. 2002; 124(44):13114-20. DOI: 10.1021/ja0207347. View

14.

WACK H, Taggi A, Hafez A, Drury 3rd W, Lectka T . Catalytic, asymmetric alpha-halogenation. J Am Chem Soc. 2001; 123(7):1531-2. DOI: 10.1021/ja005791j. View

15.

Denton R, Tang X, Przeslak A . Catalysis of phosphorus(V)-mediated transformations: dichlorination reactions of epoxides under Appel conditions. Org Lett. 2010; 12(20):4678-81. DOI: 10.1021/ol102010h. View

16.

Shibuya G, Kanady J, Vanderwal C . Stereoselective dichlorination of allylic alcohol derivatives to access key stereochemical arrays of the chlorosulfolipids. J Am Chem Soc. 2008; 130(37):12514-8. DOI: 10.1021/ja804167v. View

17.

Ciminiello P, Fattorusso E, Forino M, Di Rosa M, Ianaro A, Poletti R . Structural elucidation of a new cytotoxin isolated from mussels of the Adriatic sea. J Org Chem. 2001; 66(2):578-82. DOI: 10.1021/jo001437s. View

18.

Whitehead D, Yousefi R, Jaganathan A, Borhan B . An organocatalytic asymmetric chlorolactonization. J Am Chem Soc. 2010; 132(10):3298-300. PMC: 2883568. DOI: 10.1021/ja100502f. View

19.

Yoshimitsu T, Fukumoto N, Nakatani R, Kojima N, Tanaka T . Asymmetric total synthesis of (+)-hexachlorosulfolipid, a cytotoxin isolated from Adriatic mussels. J Org Chem. 2010; 75(16):5425-37. DOI: 10.1021/jo100534d. View

20.

Davie E, Mennen S, Xu Y, Miller S . Asymmetric catalysis mediated by synthetic peptides. Chem Rev. 2007; 107(12):5759-812. DOI: 10.1021/cr068377w. View