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. 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.

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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
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Scheme 18
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