Asymmetric Michael Addition of Dimethyl Malonate to 2 Cyclopenten-1-one Catalyzed by a Heterobimetallic Complex

To illustrate the general principle of asymmetric organocatalysis of chiral bicyclic guanidine, a density functional theory study was carried out to examine the catalytic mechanism, activation mode, origin of stereoselectivity of a [5,5]-bicyclic guanidine-catalyzed Michael addition of dimethyl malonate to 2-cyclopenten-1-one. Two types of bifunctional activation modes were examined: Brønsted acid and Brønsted-Lewis acid. The calculated enantioselectivity (ee), based on eight C–C bond forming transition states and their pre-transition state complexes, is in excellent accord with experimental result. The ternary pre-transition state complexes are stable species, which strongly influence the stereoselectivity. Similar to enzyme catalysis, the bicyclic guanidinium catalyst plays an essential recognition role in assembling the substrates together via hydrogen bonds, multiple C–H···O interactions (as oxyanion hole), donor–acceptor, and electrostatic interactions.

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A new C2-symmetric heterobimetallic complex as a promoter for asymmetric Michael addition reactions

Tetrahedron Asymmetry ◽

10.1016/s0957-4166(97)00234-6 ◽

1997 ◽

Vol 8 (13) ◽

pp. 2271-2278 ◽

Cited By ~ 40

Author(s):

G. Manickam ◽

G. Sundararajan

Keyword(s):

Michael Addition ◽

Addition Reactions ◽

Heterobimetallic Complex ◽

Asymmetric Michael Addition

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Pyrrolidinyl-Camphor Derivatives as a New Class of Organocatalyst for Direct Asymmetric Michael Addition of Aldehydes and Ketones to β-Nitroalkenes

Chemistry - A European Journal ◽

10.1002/chem.201000483 ◽

2010 ◽

Vol 16 (23) ◽

pp. 7030-7038 ◽

Cited By ~ 69

Author(s):

Ying-Fang Ting ◽

Chihliang Chang ◽

Raju Jannapu Reddy ◽

Dhananjay R. Magar ◽

Kwunmin Chen

Keyword(s):

Michael Addition ◽

New Class ◽

Asymmetric Michael Addition ◽

Aldehydes And Ketones ◽

Camphor Derivatives

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ChemInform Abstract: Asymmetric Michael Addition of Ketones to Nitroolefins: Pyrrolidinyl-oxazole-carboxamides as New Efficient Organocatalysts.

ChemInform ◽

10.1002/chin.201512034 ◽

2015 ◽

Vol 46 (12) ◽

pp. no-no

Author(s):

Ahmed Kamal ◽

Manda Sathish ◽

Vunnam Srinivasulu ◽

Jadala Chetna ◽

Kunta Chandra Shekar ◽

...

Keyword(s):

Michael Addition ◽

Asymmetric Michael Addition

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Synthesis of new pyrrolidine-based organocatalysts and study of their use in the asymmetric Michael addition of aldehydes to nitroolefins

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.13.59 ◽

2017 ◽

Vol 13 ◽

pp. 612-619 ◽

Cited By ~ 1

Author(s):

Alejandro Castán ◽

Ramón Badorrey ◽

José A Gálvez ◽

María D Díaz-de-Villegas

Keyword(s):

Michael Addition ◽

Bulky Substituent ◽

Asymmetric Michael Addition ◽

Iodination Reaction ◽

Chiral Imines ◽

New Compounds ◽

The Michael Addition

New pyrrolidine-based organocatalysts with a bulky substituent at C2 were synthesized from chiral imines derived from (R)-glyceraldehyde acetonide by diastereoselective allylation followed by a sequential hydrozirconation/iodination reaction. The new compounds were found to be effective organocatalysts for the Michael addition of aldehydes to nitroolefins and enantioselectivities up to 85% ee were achieved.

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