Journal
CHEMICAL SCIENCE
Volume 9, Issue 11, Pages 2898-2908Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7sc04430e
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Funding
- NIH [GM110525]
- NSF [CHE-1362812]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1362812] Funding Source: National Science Foundation
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Though (DHQD)(2)PHAL-catalyzed chlorocyclizations of 1,1-disubstituted olefins show useful (and in some cases, reversible) asymmetric induction, stereochemically complete descriptions of these alkene additions have remained largely unknown. Herein, based on a combination of NMR, derivative, isotope labeling, and computational studies, we present detailed stereochemical analyses of chlorocyclizations of nucleophile-tethered 1,1-disubstituted styryl systems. The selectivities of the two asymmetric bond-forming processes, namely electrophilic chlorine attack and nucleophilic ring closure, are thus mapped out independently. Under the established optimal conditions, four related chlorocyclizations were subjected to this analysis. All showed a strong preference for Cl+ delivery from the same face of the alkene. However, depending on reaction conditions and substrate identity (carboxylic acid, amide or carbamate), the internal nucleophiles may close with a strong net preference for either syn or anti addition relative to the Cl atom. Studies of both uncatalyzed and (DHQD)(2)PHAL-catalyzed processes place new boundary conditions on the role of the catalyst in these reactions.
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