Abstract
Since the discovery of molecular chirality, nonsuperimposable mirror-image organic molecules have been found to be essential across biological and chemical processes and increasingly in materials science. Generally, carbon centers containing four different substituents are configurationally stable, unless bonds to the stereogenic carbon atom are broken and re-formed. Herein, we describe sp3-stereogenic carbon-bearing molecules that dynamically isomerize, interconverting between enantiomers without cleavage of a constituent bond, nor through remote functional group migration. The stereodynamic molecules were designed to contain a pair of redox-active substituents, quinone and hydroquinone groups, which allow the enantiomerization to occur via redox-interconversion. In the presence of an enantiopure host, these molecules undergo a deracemization process that allows observation of enantiomerically enriched compounds. This work reveals a fundamentally distinct enantiomerization pathway available to chiral compounds, coupling redox-interconversion to chirality.
| Original language | English |
|---|---|
| Pages (from-to) | 15239-15244 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 42 |
| DOIs | |
| Publication status | Published - Oct 25 2017 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Stereodynamic Quinone-Hydroquinone Molecules That Enantiomerize at sp3-Carbon via Redox-Interconversion. / Kim, Byoungmoo; Storch, Golo; Banerjee, Gourab; Mercado, Brandon Q.; Castillo-Lora, Janelle; Brudvig, Gary W; Mayer, James M.; Miller, Scott J.
In: Journal of the American Chemical Society, Vol. 139, No. 42, 25.10.2017, p. 15239-15244.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stereodynamic Quinone-Hydroquinone Molecules That Enantiomerize at sp3-Carbon via Redox-Interconversion
AU - Kim, Byoungmoo
AU - Storch, Golo
AU - Banerjee, Gourab
AU - Mercado, Brandon Q.
AU - Castillo-Lora, Janelle
AU - Brudvig, Gary W
AU - Mayer, James M.
AU - Miller, Scott J.
PY - 2017/10/25
Y1 - 2017/10/25
N2 - Since the discovery of molecular chirality, nonsuperimposable mirror-image organic molecules have been found to be essential across biological and chemical processes and increasingly in materials science. Generally, carbon centers containing four different substituents are configurationally stable, unless bonds to the stereogenic carbon atom are broken and re-formed. Herein, we describe sp3-stereogenic carbon-bearing molecules that dynamically isomerize, interconverting between enantiomers without cleavage of a constituent bond, nor through remote functional group migration. The stereodynamic molecules were designed to contain a pair of redox-active substituents, quinone and hydroquinone groups, which allow the enantiomerization to occur via redox-interconversion. In the presence of an enantiopure host, these molecules undergo a deracemization process that allows observation of enantiomerically enriched compounds. This work reveals a fundamentally distinct enantiomerization pathway available to chiral compounds, coupling redox-interconversion to chirality.
AB - Since the discovery of molecular chirality, nonsuperimposable mirror-image organic molecules have been found to be essential across biological and chemical processes and increasingly in materials science. Generally, carbon centers containing four different substituents are configurationally stable, unless bonds to the stereogenic carbon atom are broken and re-formed. Herein, we describe sp3-stereogenic carbon-bearing molecules that dynamically isomerize, interconverting between enantiomers without cleavage of a constituent bond, nor through remote functional group migration. The stereodynamic molecules were designed to contain a pair of redox-active substituents, quinone and hydroquinone groups, which allow the enantiomerization to occur via redox-interconversion. In the presence of an enantiopure host, these molecules undergo a deracemization process that allows observation of enantiomerically enriched compounds. This work reveals a fundamentally distinct enantiomerization pathway available to chiral compounds, coupling redox-interconversion to chirality.
UR - http://www.scopus.com/inward/record.url?scp=85032289791&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85032289791&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b09176
DO - 10.1021/jacs.7b09176
M3 - Article
C2 - 28931280
AN - SCOPUS:85032289791
VL - 139
SP - 15239
EP - 15244
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 42
ER -