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Organo-di-Lithio Reagents: Cooperative Effect and Synthetic Applications

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Organo-di-Metallic Compounds (or Reagents)

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 47))

Abstract

The development of organometallic reagents remains one of the most important frontiers in synthetic chemistry. In this review, we summarize our research on the structures, reactions, and synthetic applications of 1,4-dilithio-1,3-butadienes as organo-di-lithio reagents. The 1,4-dilithio-1,3-butadienes bearing a wide variety of substitution patterns on the butadienyl skeleton can be readily prepared in high efficiency. The configuration has been predicted and demonstrated to favor a double dilithium bridging structure in both solution and solid states. The two Li atoms are bridged by a butadiene moiety and are in close proximity. By taking advantage of this unique configuration, we have developed useful and interesting synthetic methodologies. Three types of reactions of 1,4-dilithio-1,3-butadienes have been developed and are discussed: intramolecular reaction, intermolecular reaction, and transmetallation. First, intramolecular reaction is introduced as a result of the intra-cooperative effect among the two C–Li moieties, the butadienyl bridge, and the substituents. A useful transformation from silylated 1,4-dilithio-1,3-butadienes to α-lithio siloles is described. Second, we discuss an intermolecular reaction that results from the inter-cooperative effect of the two C–Li moieties toward substrates. The intermolecular reactions are featured with formation of oxy-cyclopentadienyl dilithium via the reaction of di-lithio reagents with CO and formation of a series of N-heterocycles via the reaction of di-lithio reagents with nitriles. Third, we discuss transmetallation of di-lithio reagents with aluminum, copper, iron, zinc, or barium salts to generate diversified organo-di-metallic or metallacyclic compounds. The dimetallic 1,4-dilithio-1,3-butadienes and their transmetallated derivatives provide unique synthetic organometallic reagents that are different from monometallic reagents, both in terms of reactivity and in synthetic application. These organo-di-metallic reagents provide the access to interesting and useful compounds that are not available by other means, such as N-, O-, and Si-containing heterocycles, strained ring systems, metal-containing macrocycles, and metal complexes bearing new types of ligand.

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Abbreviations

Ac:

Acetyl

Ad:

Adamantyl

Ar:

Aryl

Bn:

Benzyl

Bu:

Butyl

cat:

Catalyst

cod:

Cyclooctadiene

COT:

Cyclooctatetraene

Cp:

Cyclopentadienyl

DMAD:

Dimethyl azodicarboxylate

DME:

1,2-Dimethoxyethane

DMF:

Dimethylformamide

DMPU:

1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone

DMSO:

Dimethyl sulfoxide

dppe:

1,2-Bis(diphenylphosphino)ethane

ee:

Enantiomer excess

equiv:

Equivalent(s)

Et:

Ethyl

h:

Hour(s)

Hex:

Hexyl

HMPA:

Hexamethylphosphoric triamide

i-Pr:

Isopropyl

LDA:

Lithium diisopropylamide

Me:

Methyl

min:

Minute(s)

mol:

Mole(s)

NBS:

N-bromosuccinimide

NCS:

N-chlorosuccinimide

Nu:

Nucleophile

Ph:

Phenyl

Pr:

Propyl

py:

Pyridine

rt:

Room temperature

s:

Second(s)

TBAF:

Tetrabutylammonium fluoride

t-Bu:

Tert-butyl

THF:

Tetrahydrofuran

TIPS:

Triisopropylsilyl

TMEDA:

N,N,N′,N′-Tetramethyl- 1,2-ethylenediamine

TMS:

Trimethylsilyl

Tol:

4-Methylphenyl

Ts:

4-toluenesulfonyl

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  1. College of Chemistry, Peking University, Beijing, 100871, China

    Shaoguang Zhang, Wen-Xiong Zhang & Zhenfeng Xi

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    Zhenfeng Xi

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Zhang, S., Zhang, WX., Xi, Z. (2013). Organo-di-Lithio Reagents: Cooperative Effect and Synthetic Applications. In: Xi, Z. (eds) Organo-di-Metallic Compounds (or Reagents). Topics in Organometallic Chemistry, vol 47. Springer, Cham. https://doi.org/10.1007/3418_2013_71

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