The origin of enantioselectivity in the l-threonine-derived phosphine–sulfonamide catalyzed aza-Morita–Baylis–Hillman reaction: effects of the intramolecular hydrogen bonding

L-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to eluc...

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Published inOrganic & biomolecular chemistry Vol. 11; no. 29; pp. 4818 - 4824
Main Authors Lee, Richmond, Zhong, Fangrui, Zheng, Bin, Meng, Yuezhong, Lu, Yixin, Huang, Kuo-Wei
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 07.08.2013
Subjects
Aza Compounds - chemical synthesis
Aza Compounds - chemistry
Catalysis
Chemistry
Chemistry, Organic
Hydrogen Bonding
Phosphines - chemistry
Physical Sciences
Quantum Theory
Science & Technology
Stereoisomerism
Sulfonamides - chemistry
Threonine - chemistry
ELECTROSPRAY-IONIZATION MASS
ASYMMETRIC-SYNTHESIS
LEWIS-BASES
HILIMAN REACTION
KINETIC RESOLUTION
3+2 ANNULATIONS
METHYL VINYL KETONE
BICYCLIC PHOSPHOLANES
ACTIVATED OLEFINS
BIFUNCTIONAL ORGANOCATALYSTS
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Summary:L-Threonine-derived phosphine-sulfonamide 4 was identified as the most efficient catalyst to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions, affording the desired aza-MBH adducts with excellent enantioselectivities. Density functional theory (DFT) studies were carried out to elucidate the origin of the observed enantioselectivity. The importance of the intramolecular N-H center dot center dot center dot O hydrogen-bonding interaction between the sulfonamide and enolate groups was identified to be crucial in inducing a high degree of stereochemical control in both the enolate addition to imine and the subsequent proton transfer step, affording aza-MBH reactions with excellent enantioselectivity.
Bibliography:ObjectType-Article-1
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ISSN:1477-0520
1477-0539
1477-0539
DOI:10.1039/c3ob40144h