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. 2014 Jan 3;79(1):140-71.
doi: 10.1021/jo4023765. Epub 2013 Dec 11.

Catalytic, enantioselective, intramolecular carbosulfenylation of olefins. Preparative and stereochemical aspects

Scott E Denmark  1 , Alex Jaunet
Affiliations

Catalytic, enantioselective, intramolecular carbosulfenylation of olefins. Preparative and stereochemical aspects

Scott E Denmark et al. J Org Chem. .

Abstract

The first catalytic, enantioselective, intramolecular carbosulfenylation of isolated alkenes with aromatic nucleophiles is described. The combination of N-phenylsulfenylphthalimide, a chiral selenophosphoramide derived from BINAM, and ethanesulfonic acid as a cocatalytic Brønsted acid induced an efficient and selective cyclofunctionalization of various alkenes (aliphatic and aromatic) tethered to a 3,4-methylenedioxyphenyl ring. Under these conditions, 6-phenylthio-5,6,7,8-tetrahydronaphthalenes are formed diastereospecifically in good yields (50-92%) and high enantioselectivities (71:29-97:3 er). E-Alkenes reacted much more rapidly and with much higher selectivity than Z-alkenes, whereas electron-rich alkenes reacted more rapidly but with comparable selectivity to electron-neutral alkenes and electron-deficient alkenes. The Brønsted acid played a critical role in effecting reproducible enantioselectivity. A model for the origin of enantioselectivity and the dependence of rate and selectivity on alkene structure is proposed along with a rationale for the site selectivity in reactions with monoactivated arene nucleophiles.

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Figures

Figure 1
Figure 1
Products of unexpected side reactions.
Figure 2
Figure 2
Configurations of trans-2a and cis-2a.
Figure 3
Figure 3
Proposed catalytic cycle for sulfenofunctionalization.
Figure 4
Figure 4
X-ray crystallographic structure of (S)-17a and proposed models for the geometry of the catalytically active species i.
Figure 5
Figure 5
The spiro and planar transition states for the thiiranium ion formation.
Figure 6
Figure 6
Proposed rationale for the unselective formation of thiiranium ions from Z-alkenes.
Figure 7
Figure 7
Proposed rationale for the selective formation of thiiranium ions from E-alkenes.
Figure 8
Figure 8
Proposed rationale for thiiranium ion formation from branched E-alkenes.
Figure 9
Figure 9
Electrostatic charge (natural charge values) and local energies of HOMO orbitals for models 36 and 37.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
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Scheme 9
Scheme 9
Scheme 10
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Scheme 11
Scheme 11
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References

    1. de la Mare PBD, Bolton R. In: Electrophilic Additions to Unsaturated Systems. 2nd Ed. de la Mare PBD, Bolton R, editors. Vol. 9. Elsevier; Amsterdam: 1982. pp. 198–246.
    1. Schmid GH. Supplement A: The chemistry of double-bonded functional groups. (Part 1) 1989;Volume 2:679–731.
    2. Schmid GH, Garratt DG. The chemistry of double-bonded functional groups Part 2. John Wiley & Sons; London: 1977. pp. 725–912.
    3. Lucchini V, Modena G, Pasquato L. Gazz. Chim. Ital. 1997;127(4):177–188.
    4. Rayner CM. In: Organosulfur Chemistry: Synthetic Aspects. Page P, editor. Academic Press; London: 1995. pp. 89–131.
    5. Modena G, Pasquato L, Lucchini V. Phosphorus, Sulfur Silicon Relat. Elem. 1994;95–6(1–4):265–282.
    6. Capozzi G, Modena G, Pasquato L. In: The Chemistry of Sulphenic Acids and Their Derivatives. Patai S, editor. John Wiley & Sons Ltd; West Sussex: 1990. pp. 403–516.
    7. Harring SR, Edstrom ED, Livinghouse T. Adv. Heterocyclic Nat. Prod. Synth. 1992;2:299–376.
    8. Capozzi G, Modena G. In: Organic Sulfur Chemistry: Theoretical and Experimental Advances. Bernardi F, Csizmadia IG, Mangini A, editors. Vol. 19. Elsevier; Amsterdam: 1985. pp. 246–298.
    9. Mueller WH. Angew. Chem. Int. Ed. 1969;8:482–492.
    1. Drabowicz J, Lyzwa P, Mikolajczyk M. In: The Chemistry of Sulphenic Acids and Their Derivatives. Patai S, editor. John Wiley & Sons Ltd; West Sussex: 1990. pp. 187–220.
    2. Drabowicz J, Kielbasinski P, Mikolajczyk M. In: The Chemistry of Sulphenic Acids and Their Derivatives. Patai S, editor. John Wiley & Sons Ltd; West Sussex: 1990. pp. 221–292.
    1. Hogg DR. In: The Chemistry of Sulphenic Acids and Their Derivatives. Patai S, editor. John Wiley & Sons Ltd; West Sussex: 1990. pp. 361–402.
    1. Fox DJ, House D, Warren S. Angew. Chem., Int. Ed. 2002;41:2462–2482. - PubMed

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