The effect of pre-existing stereocenters in the intramolecular asymmetric Stetter reaction

Reynolds, Nathan T.; Rovis, Tomislav

doi:10.1016/j.tet.2005.03.121

Cited by 60 publications

(29 citation statements)

References 20 publications

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“…( RS )-Tetrahydro-4-methylpyran-2-one39 (0.410 g, 3.59 mmol) was treated with a saturated solution of anhydrous HBr in EtOH (15 mL), and the mixture was stirred at rt for 3 d (TLC in T2). The reaction was quenched by pouring it into 200 mL of water and extracting it with Et 2 O(3 × 50 mL).…”

Section: Methodsmentioning

confidence: 99%

Structure−Activity Study of New Inhibitors of Human Betaine-Homocysteine S-Methyltransferase

et al. 2009

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Betaine-homocysteine S-methyltransferase (BHMT) catalyzes the transfer of a methyl group from betaine to L-homocysteine, yielding dimethylglycine and L-methionine. In this study, we prepared a new series of BHMT inhibitors. The inhibitors were designed to mimic the hypothetical transition state of BHMT substrates and consisted of analogues with NH, N(CH 3 ), or N(CH 3 ) 2 groups separated from the homocysteine sulfur atom by a methylene, ethylene, or a propylene spacer. Only the inhibitor with the N(CH 3 ) moiety and ethylene spacer gave moderate inhibition. This result led us to prepare two inhibitors lacking a nitrogen atom in the S-linked alkyl chain: (RS,RS)-5-(3-amino-3-carboxypropylthio)-3-methylpentanoic acid and (RS)-5-(3-amino-3-carboxypropylthio)-3,3-dimethylpentanoic acid. Both of these compounds were highly potent inhibitors of BHMT. The finding that BHMT does not tolerate a true betaine mimic within these inhibitors, especially the nitrogen atom, is surprising and evokes questions about putative conformational changes of BHMT upon the binding of the substrates/products and inhibitors.

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Section: Methodsmentioning

confidence: 99%

Structure−Activity Study of New Inhibitors of Human Betaine-Homocysteine S-Methyltransferase

et al. 2009

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“…The influence of stereocenters in the backbone has been investigated [74]. A racemic substrate 101 can be subjected to standard Stetter reaction conditions leading to disubstituted cyclopentanones 102 .…”

Section: Stetter Reactionmentioning

confidence: 99%

Carbene Catalysts

Moore

Rovis

2009

Topics in Current Chemistry

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“…Investigation of the aliphatic substrates led us to probe the effects that a pre-existing stereocenter would have on the asymmetric intramolecular Stetter reaction 48. With this in mind we evaluated the impact of substitution at each position between the aldehyde and the tethered Michael acceptor (substrates are racemates).…”

Section: The Effect Of Pre-existing Stereocenters In the Intramolementioning

confidence: 99%

The Catalytic Asymmetric Intramolecular Stetter Reaction

Alaniz¹,

Rovis²

2009

Synlett

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This account chronicles our efforts at the development of a catalytic asymmetric Stetter reaction using chiral triazolium salts as small molecule organic catalysts. Advances in the mechanistically related azolium-catalyzed asymmetric benzoin reaction are discussed, particularly as they apply to catalyst design. A chronological treatise of reaction discovery, catalyst optimization and reactivity extension follows.

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The effect of pre-existing stereocenters in the intramolecular asymmetric Stetter reaction

Cited by 60 publications

References 20 publications

Structure−Activity Study of New Inhibitors of Human Betaine-Homocysteine S-Methyltransferase

Structure−Activity Study of New Inhibitors of Human Betaine-Homocysteine S-Methyltransferase

Carbene Catalysts

The Catalytic Asymmetric Intramolecular Stetter Reaction

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