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The Effect of Confo...
The Effect of Conformational Freedom vs Restriction on the Rate in Asymmetric Hydrogenation : Iridium-Catalyzed Regio- and Enantioselective Monohydrogenation of Dienones
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- Zheng, Jia (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Peters, Bram B. C., 1994- (author)
- Stockholms universitet,Institutionen för organisk kemi
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- Jiang, Wei (author)
- Stockholms universitet,Institutionen för organisk kemi
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Suarez, Lluis Artus (author)
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Ahlquist, Marten S. G. (author)
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Singh, Thishana (author)
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- Andersson, Pher G., 1963- (author)
- Stockholms universitet,Institutionen för organisk kemi
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(creator_code:org_t)
- 2024
- 2024
- English.
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In: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 30:13
- Related links:
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https://doi.org/10.1...
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https://urn.kb.se/re...
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Abstract
Subject headings
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- Transition metal-catalyzed asymmetric hydrogenation constitutes an efficient strategy for the preparation of chiral molecules. When dienes are subjected to hydrogenation, control over regioselectivity still presents a large challenge and the fully saturated alkane is often yielded. A few successful monohydrogenations of dienes have been reported, but hitherto these are only efficient for dienes comprised of two distinctly different olefins. Herein, the reactivity of a conjugated carbonyl compound as a function of their conformational freedom is studied, based on a combined experimental and theoretical approach. It was found that alkenes in the (s)-cis conformation experience a large rate acceleration while (s)-trans restrained alkenes undergo hydrogenation slowly. Ultimately, this reactivity aspect was exploited in a novel method for the monohydrogenation of dienes based on conformational restriction ((s)-cis vs (s)-trans). This mode of discrimination conceptually differs from existing monohydrogenations and dienones constructed of two olefins similar in nature could efficiently be hydrogenated to the chiral alkene (up to 99 % ee). The extent of regioselection is even powerful enough to overcome the conventional reactivity order of substituted olefins (di>tri>tetra). This high yielding and atom-economical protocol provides an interesting opportunity to instal a stereogenic center on a carbocycle, while leaving a synthetically useful alkene untouched.
Subject headings
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Keyword
- Dienes
- Hydrogenation
- Iridium catalysis
- Monohydrogenation
- Regioselectivity
Publication and Content Type
- ref (subject category)
- art (subject category)
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