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Chiral Brønsted Acids for Asymmetric Organocatalysis

Part of the Topics in Current Chemistry book series (TOPCURRCHEM,volume 291)

Abstract

Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

Keywords

  • Asymmetric catalysis
  • BINOL
  • Dicarboxylic acids
  • N-Triflyl phosphoramides
  • Phosphoric acids
  • Strong chiral Brønsted acids

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Scheme 1
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Fig. 16
Scheme 67
Scheme 68
Scheme 69
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Scheme 73
Scheme 74
Scheme 75
Scheme 76

Notes

  1. 1.

    pK a (dimethyl phosphate) = 1.29, pK a (acetic acid ) = 4.76

  2. 2.

    for example: pKa (PhOH) = 18.0, pKa (PhSH) = 10.3, pKa (PhSeH) = 7.1

Abbreviations

Ac:

Acetyl

All:

Allylic substituent

Ar:

Aromatic substituent

BHT:

Butylated hydroxytoluene

BINAM:

2,2′-Diamino-1,1′-binaphthyl

BINOL:

1,1′-Binaphthol

bmim:

1-Butyl-3-methylimidazolium

Bn:

Benzyl

Boc:

tert-Butyloxycarbonyl

Bs:

Brosyl

tBu:

tert-Butyl

BV:

Baeyer-Villiger

Bz:

Benzoyl

cat:

Catalytic

Cbz:

Benzyloxycarbonyl

CSA:

Camphorsulfonic acid

Cy:

Cyclohexyl

DA:

Diels-Alder

DBU:

1,5-Diazabicyclo[1.4.0]undec-5-ene

DCE:

1,2-Dichloroethane

DFT:

Density functional theory

DHP:

1,4-Dihydropyridine

DHPM:

3,4-Dihydropyrimidin-2-(1H)-one

DMAP:

4-Dimethylaminopyridine

dr :

Diasteriomeric ratio

ee :

Enantiomeric excess

equiv:

Equivalent(s)

Et:

Ethyl

EWG:

Electron-withdrawing group

h:

Hour(s)

HX:

Brønsted acid

HX*:

Chiral Brønsted acid

k:

Rate constant

M:

Metal

MCR:

Multicomponent reaction

Me:

Methyl

Mes:

Mesityl

min:

Minute(s)

MS:

Molecular sieves

NADH:

Nicotinamide adenine dinucleotide

Np:

Naphthyl

NuH:

Nucleophile

p :

Para

Pent:

n-Pentyl

Ph:

Phenyl

PMB:

para-Methoxybenzyl

PMP:

para-Methoxyphenye

cPr:

Cyclopropyl

cPr:

Isopropyl

R:

Organic substituent

rac:

Racemic

RT:

Room temperature

TADDOL:

α,α,α′,α′-Tetraaryl-1,3-dioxolane-4,5-dimethanol

tert :

Tertiary

Tf:

Triflyl (trifluoromethanesulfonyl)

TMS:

Trimethylsilyl

TS:

Transition state

Ts:

Tosyl

VAPOL:

4,4′-Dihydroxy-2,2′-diphenyl-3,3′-biphenanthryl

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Acknowledgments

We thank Dr. Pilar García García and Steffen Müller for proofreading the manuscript. B.L. thanks the current and previous members of his group for their contributions to the field of asymmetric Brønsted acid catalysis. Generous support by the Max Planck Society, the Deutsche Forschungsgemeinschaft (Priority Program Organocatalysis SPP1179), and the Fonds der Chemischen Industrie (Kekulé fellowship to C.M.R., Silver Award to B.L.) is gratefully acknowledged.

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Kampen, D., Reisinger, C.M., List, B. (2010). Chiral Brønsted Acids for Asymmetric Organocatalysis. In: List, B. (eds) Asymmetric Organocatalysis. Topics in Current Chemistry, vol 291. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-02815-1_1

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