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Iridium-Catalyzed Asymmetric Allylic Substitutions

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Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 38))

Abstract

Ir-catalyzed asymmetric allylic substitution reactions have been reviewed. This chapter discusses respectively the mechanistic investigation, reaction scope, and synthetic application of Ir-catalyzed allylic substitution reactions. The reaction scope is classified according to different types of nucleophiles such as C, N, O, and S.

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Abbreviations

Ac:

Acetyl

BINOL:

Binaphthol

Bn:

Benzyl

Boc:

tert-Butoxycarbonyl

BSA:

N,O-Bis(trimethylsilyl)acetamide

Bz:

Benzoyl

Cbz:

Benzyloxycarbonyl

cod:

1,5-Cyclooctadiene

coe:

Cyclooctene

DABCO:

1,4-Diazabicyclo[2.2.2]octane

dbcot:

Dibenzo[a,e]cyclooctatetraene

DBU:

1,8-Diazabicyclo[5.4.0]undec-7-ene

DCM:

Dichloromethane

de:

Diastereomeric excess

DMAP:

N,N-Dimethylaminopyridine

DME:

1,2-Dimethoxy ethane

DMF:

Dimethylformamide

e.s.:

Enantiospecificity

ee:

Enantiomeric excess

Fmoc:

9-Fluorenylmethyloxycarbonyl

LDA:

Lithium diisopropylamide

Ms:

Methanesulfonyl

MS:

Molecular sieves

Ns:

Nitrophenylsulfonyl

PS:

Proton sponge

RCM:

Ring closing metathesis

TBAF:

Tetrabutyl ammonium fluoride

TBD:

1,5,7-Triazabicyclo-[4.4.0]dec-5-ene

TBDPS:

tert-Butyldiphenylsilyl

TBS:

tert-Butyldimethylsilyl

TEA:

Triethylamine

Teoc:

2-(Trimethylsilyl)ethoxy carbonyl

TES:

Triethylsilyl

Tf:

Trifluoromethanesulfonyl

THF:

Tetrahydrofuran

THT:

Tetrahydrothiophene

TIPS:

Triisopropylsilyl

TM:

Transition metal

TMS:

Trimethylsilyl

Troc:

2,2,2-Trichlorethoxycarbonyl

Ts:

p-Toluenesulfonyl

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Acknowledgments

Financial support was provided by Chinese Academy of Sciences, National Natural Science Foundation of China (20872159, 20821002), and National Basic Research Program of China (973 Program 2009CB825300). We thank Prof. Wei Zhang for assisting in the preparation of the manuscript.

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Authors and Affiliations

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China

    Wen-Bo Liu, Ji-Bao Xia & Shu-Li You

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  1. Wen-Bo Liu
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  2. Ji-Bao Xia
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Correspondence to Shu-Li You .

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  1. Inst. Organische Chemie, Universität des Saarlandes, Gebäude C 4.2, Saarbrücken, 66123, Germany

    Uli Kazmaier

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Liu, WB., Xia, JB., You, SL. (2011). Iridium-Catalyzed Asymmetric Allylic Substitutions. In: Kazmaier, U. (eds) Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis. Topics in Organometallic Chemistry, vol 38. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2011_10

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