Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2010 Nov 10;132(44):15752-65.
doi: 10.1021/ja106837b.

Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions

Scott E Denmark  1 , Dipannita Kalyani, William R Collins
Affiliations

Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions

Scott E Denmark et al. J Am Chem Soc. .

Abstract

A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Hypothetical catalytic cycle for Lewis base catalyzed selenofunctionalization of olefins.
Figure 2
Figure 2
Catalytic asymmetric selenoetherification with BINAM derived thiophosphoramides.
Figure 3
Figure 3
Hypervalent bonding between the nitro group and the selenium center in 2-nitrobenzeneselenenyl halides.
Figure 4
Figure 4
Proposed catalytic cycle for Lewis base catalyzed selenoetherification.
Figure 5
Figure 5
Transition structure hypothesis for catalytic asymmetric selenoetherification.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Scheme 3
Scheme 3
Scheme 4
Scheme 4
Scheme 5
Scheme 5
Scheme 6
Scheme 6
Scheme 7
Scheme 7
Scheme 8
Scheme 8
Scheme 9
Scheme 9
Scheme 10
Scheme 10
Scheme 11
Scheme 11
Scheme 12
Scheme 12
Scheme 13
Scheme 13
Scheme 14
Scheme 14
Scheme 15
Scheme 15
Scheme 16
Scheme 16
Scheme 17
Scheme 17
Scheme 18
Scheme 18
See this image and copyright information in PMC

References

    1. Nicolaou KC, Petasis NA. Selenium in Natural Product Synthesis. CIS; Philadelphia: 1984.
    2. Paulmier C. Selenium Reagents and Intermediates in Organic Synthesis. Pergamon Press; Oxford: 1986.
    3. Liotta D, editor. Organoselenium Chemistry. Chap 1–2. Wiley; New York: 1987. pp. 1–163.
    4. Back TG. In: The Chemistry of Organic Selenium and Tellurium Compounds. Patai S, editor. Vol. 2. Wiley; New York: 1987. pp. 94–215.
    5. Back TG, editor. In Organoselenium Chemistry - A Practical Approach. Oxford University Press; Oxford: 1999.
    6. Tiecco M. In: Topics in Current Chemistry: Organoselenium Chemistry. Wirth T, editor. Springer; Heidelberg: 2000. pp. 7–54.
    7. Petragnani N, Stefani HA, Valduga CJ. Tetrahedron. 2001;57:1411–1448.
    8. Ranganathan S, Muraleedharan KM, Vaish NK, Jayaraman N. Tetrahedron. 2004;60:5273–5308.
    1. Schmid GH, Garratt DG. Tetrahedron. 1978;34:2869–2872.
    2. Luh TY, So WH, Cheung KS, Tam SW. J Org Chem. 1985;50:3051–3053.
    1. Hassner A, Amarasekara AS. Tetrahedron Lett. 1987;28:5185–5188.
    1. Denis JN, Vicens J, Krief A. Tetrahedron Lett. 1979;29:2697–2700.
    2. Scarborough RM, Smith AB, Barnette WE, Nicolaou KC. J Org Chem. 1979;44:1742–1744.
    1. Kozikowski AP, Sorgi KL, Schmiesing RJ. J Chem Soc, Chem Commun. 1980:477–479.

Publication types