Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates

Catalytic carbene insertion into C-H bonds.

Synergistic catalysis is a synthetic strategy wherein both the nucleophile and the electrophile are simultaneously activated by two separate and distinct catalysts to afford a single chemical transformation. This powerful catalysis strategy leads to several benefits, specifically synergistic catalysis can (i) introduce new, previously unattainable chemical transformations, (ii) improve the efficiency of existing transformations, and (iii) create or improve catalytic enantioselectivity where stereocontrol was previously absent or challenging. This perspective aims to highlight these benefits using many of the successful examples of synergistic catalysis found in the literature.

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Synergistic catalysis: A powerful synthetic strategy for new reaction development

Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for catalytic, enantioselective synthesis. This review describes developments in the burgeoning field of asymmetric ion-pairing catalysis with an emphasis on the insights that have been gleaned into the structural and mechanistic features that contribute to high asymmetric induction.

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Asymmetric ion-pairing catalysis.

In recent years, the concept of combining transition metal catalysis and organocatalysis has emerged as a promising strategy for developing new and valuable reactions, and has attracted considerable attention as it could potentially enable unprecedented transformations not currently possible by use of the transition metal complex or the organocatalyst alone. In this critical review, this strategy is illustrated with several recent outstanding examples, with the aim of shedding light on the synthetic utilities and potentials of this concept as a novel tool in organic synthesis (118 references).

Combining transition metal catalysis and organocatalysis: a broad new concept for catalysis

An asymmetric three-component reaction of diazo compounds and alcohols with imines catalyzed cooperatively by a rhodium complex and a chiral Bronsted acid provides a general and efficient entry to β-amino-α-hydroxyl acid derivatives in high yields with excellent stereoselectivities.

Cooperative catalysis with chiral Brønsted acid-Rh2(OAc)4: highly enantioselective three-component reactions of diazo compounds with alcohols and imines.

(R)-(+)-2,2′-Bis(methoxymethoxy)-1,1′-binaphthyl n-Butyllithium




Iodine 9-Phenanthreneboronic acid




Tetrakis(triphenylphosphine) palladium(0)




Phosphorus oxychloridea (R)-2,2′-Bis(methoxymethoxy)-3,3′-diiodo-1,1′- binaphthalene (R)-2,2′-Bis(methoxymethoxy)-3,3′-bis(9-phenanthryl)-1,1′-binaphthalene (R)-3,3′-Bis(9-phenanthryl)-1,1′-binaphthalene-2,2′-diol (R)-3,3′-Bis(9-phenanthryl)-1,1′-binaphthalene-2,2′-diyl hydrogen phosphate





Keywords:

3,3′-bis(9-phenanthryl)-1,1′-binaphthalene-2,2′-diyl hydrogen phosphate;
chiral Bronsted acid;
electrophiles;
protonation;
BINOL phosphates;
aza Diels-Alder reactions

(R)‐3,3′‐bis(9‐Phenanthryl)‐1,1′‐Binaphthalene‐2,2′‐Diyl Hydrogen Phosphate

Cooperative Catalysis with Chiral Broensted Acid-Rh2(OAc)4: Highly Enantioselective Three-Component Reactions of Diazo Compounds with Alcohols and Imines.

Wei-Jun Liu

Papers

Cooperative catalysis with chiral Brønsted acid-Rh2(OAc)4: highly enantioselective three-component reactions of diazo compounds with alcohols and imines.

(R)‐3,3′‐bis(9‐Phenanthryl)‐1,1′‐Binaphthalene‐2,2′‐Diyl Hydrogen Phosphate

Cooperative Catalysis with Chiral Broensted Acid-Rh2(OAc)4: Highly Enantioselective Three-Component Reactions of Diazo Compounds with Alcohols and Imines.