Enecarbamates as Selective Substrates in Oxidations:  Chiral-Auxiliary-Controlled Mode Selectivity and Diastereoselectivity in the [2+2] Cycloaddition and Ene Reaction of Singlet Oxygen and in the Epoxidation by DMD andmCPBA

Waldemar Adam; Sara G. Bosio; Nicholas J. Turro; Barbara T. Wolff

doi:10.1021/jo035745c

Enecarbamates as Selective Substrates in Oxidations: Chiral-Auxiliary-Controlled Mode Selectivity and Diastereoselectivity in the [2+2] Cycloaddition and Ene Reaction of Singlet Oxygen and in the Epoxidation by DMD andmCPBA

The Journal of Organic Chemistry ◽

10.1021/jo035745c ◽

2004 ◽

Vol 69 (5) ◽

pp. 1704-1715 ◽

Cited By ~ 67

Author(s):

Waldemar Adam ◽

Sara G. Bosio ◽

Nicholas J. Turro ◽

Barbara T. Wolff

Keyword(s):

Singlet Oxygen ◽

Chiral Auxiliary ◽

Ene Reaction ◽

Mode Selectivity

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Enecarbamates as Selective Substrates in Oxidations: Chiral-Auxiliary-Controlled Mode Selectivity and Diastereoselectivity in the [2 + 2] Cycloaddition and Ene Reaction of Singlet Oxygen and in the Epoxidation by DMD and mCPBA.

ChemInform ◽

10.1002/chin.200428143 ◽

2004 ◽

Vol 35 (28) ◽

Author(s):

Waldemar Adam ◽

Sara G. Bosio ◽

Nicholas J. Turro ◽

Barbara T. Wolff

Keyword(s):

Singlet Oxygen ◽

Chiral Auxiliary ◽

Ene Reaction ◽

Mode Selectivity

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Efficient π-Facial Control in the Ene Reaction of Nitrosoarene, Triazolinedione, and Singlet Oxygen with Tiglic Amides of the Bornane-Derived Sultam as Chiral Auxiliary: An Economical Synthesis of Enantiomerically Pure Nitrogen- and Oxygen-Functionalized Acrylic Acid Derivatives

Journal of the American Chemical Society ◽

10.1021/ja026640e ◽

2002 ◽

Vol 124 (44) ◽

pp. 12938-12939 ◽

Cited By ~ 24

Author(s):

Waldemar Adam ◽

Hans-Georg Degen ◽

Oliver Krebs ◽

Chantu R. Saha-Möller

Keyword(s):

Acrylic Acid ◽

Singlet Oxygen ◽

Chiral Auxiliary ◽

Pure Nitrogen ◽

Ene Reaction ◽

Enantiomerically Pure

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ChemInform Abstract: Stereoselectivity in the Ene Reaction of syn- and anti-1-(4-tert.- Butylcyclohexylidene)-4-tert.-butylcyclohexane with Singlet Oxygen, Nitrosyl Hydride, Nitrosoformaldehyde, 4-Phenyl-1,2,4-triazol-3,5- dione, Diethyl Azodicarboxylate

ChemInform ◽

10.1002/chin.199133078 ◽

2010 ◽

Vol 22 (33) ◽

pp. no-no

Author(s):

H.-S. DANG ◽

A. G. DAVIES

Keyword(s):

Singlet Oxygen ◽

Ene Reaction ◽

Nitrosyl Hydride ◽

Diethyl Azodicarboxylate

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ChemInform Abstract: Diastereoselective Synthesis of Merucathin: The Singlet Oxygen Ene Reaction (Schenck Reaction) as a Key Step Towards an E-Configurated . beta.-Amino Allylic Alcohol.

ChemInform ◽

10.1002/chin.199602295 ◽

2010 ◽

Vol 27 (2) ◽

pp. no-no

Author(s):

W. ADAM ◽

H.-G. BRUENKER

Keyword(s):

Singlet Oxygen ◽

Allylic Alcohol ◽

Diastereoselective Synthesis ◽

Ene Reaction

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ChemInform Abstract: Z-3-Alkylidene-4,5-dihydro-4-hydroxy-5-methyl-2-(3H)-furanones by Regio- and Diastereoselective Ene Reaction of Singlet Oxygen (Schenk Reaction) with γ-Hydroxy Vinylstannanes: An Enantioselective Synthesis of Dihydromahubanolide B.

ChemInform ◽

10.1002/chin.199440129 ◽

2010 ◽

Vol 25 (40) ◽

pp. no-no

Author(s):

W. ADAM ◽

P. KLUG

Keyword(s):

Singlet Oxygen ◽

Enantioselective Synthesis ◽

Ene Reaction

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Photooxygenation in polymer matrices: En route to highly active antimalarial peroxides

Pure and Applied Chemistry ◽

10.1351/pac200577061059 ◽

2005 ◽

Vol 77 (6) ◽

pp. 1059-1074 ◽

Cited By ~ 15

Author(s):

Axel G. Griesbeck ◽

Tamer T. El-Idreesy ◽

Anna Bartoschek

Keyword(s):

Singlet Oxygen ◽

Protoporphyrin Ix ◽

Polymer Matrices ◽

Allylic Alcohols ◽

Ene Reaction ◽

Highly Active ◽

Determining Factors ◽

Broad Variety ◽

Covalently Linked

Photooxygenation involving the first excited singlet state of molecular oxygen is a versatile method for the generation of a multitude of oxy-functionalized target molecules often with high regio- and stereoselectivities. The efficiency of singlet-oxygen reactions is largely dependent on the nonradiative deactivation paths, mainly induced by the solvent and the substrate intrinsically. The intrinsic (physical) quenching properties as well as the selectivity-determining factors of the (chemical) quenching can be modified by adjusting the microenvironment of the reactive substrate. Tetraarylporphyrins or protoporphyrin IX were embedded in polystyrene (PS) beads and in polymer films or covalently linked into PS during emulsion polymerization. These polymer matrices are suitable for a broad variety of (solvent-free) photooxygenation reactions. One specific example discussed in detail is the ene reaction of singlet oxygen with chiral allylic alcohols yielding unsaturated β-hydroperoxy alcohols in (threo) diastereoselectivities, which depended on the polarity and hydrogen-bonding capacity of the polymer matrix. These products were applied for the synthesis of mono- and spirobicyclic 1,2,4-trioxanes, molecules that showed moderate to high antimalarial properties. Subsequent structure optimization resulted in in vitro activities that surpassed that of the naturally occurring sesquiterpene-peroxide artemisinin.

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