Clean and convenient procedure for converting primary alkyl iodides and .alpha.,.omega.-diiodoalkanes into the corresponding alkyllithium derivatives by treatment with tert-butyllithium

Negishi, Ei‐ichi; Swanson, Douglas R.; Rousset, Christophe

doi:10.1021/jo00306a022

Cited by 203 publications

(78 citation statements)

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“…At first the bromide has to be treated with 2 equivalents of t-butyllithium to furnish via lithium-bromine exchange the corresponding organolithium compound, which can then be transformed into the GILLMAN cuprate using 0.5 equivalent of copper(I). 45,60,61,62 Iodides are even better substrates for the conversion to the corresponding cuprate because of their better capacity to undergo lithium-halogen exchange.…”

Section: Synthesis Of the Protected Acetalmentioning

confidence: 99%

Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

et al. 2007

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A modular asymmetric synthesis of the functionalized azaspirocycles 6 (m = 2, n = 1), 7 (m = 1, n = 2), 8 (m = n = 2), 12, 20, and 24 from the cyclic allylic sulfoximines 1 is described. The synthetic strategy is based on the stereoselective construction of the carbocycle 4 containing the amino-substituted tertiary C atom from 1 followed by the generation of the azaspirocycle. Three different routes have been followed for the synthesis of the heterocyclic ring: N,C-dianion cycloalkylation, ring-closing metathesis, and N-acyl iminium ion formation.

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Section: Synthesis Of the Protected Acetalmentioning

confidence: 99%

Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

et al. 2007

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“…Finally, the introduction of an exomethylene group succeeded using a Peterson protocol. [21] Initially, trimethylsilylmethyllithium [22] was added to isoquinolone 6 to give carbinol 21 in 76.6% yield as a single diastereomer. [23] A NOESY analysis proved the syn-configuration of the hydroxy group and the allyl side chain (Figure 3).…”

Section: Synthesis Of Phenanthridines and Cyclohexenesmentioning

confidence: 99%

Synthesis and Derivatization of Substituted (R)‐ and (S)‐ C‐Allylglycines

Zhang¹,

Münch²,

Nubbemeyer³

2004

Adv Synth Catal

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Various (R)-and (S)-C-allylglycine derivatives were synthesized by means of an auxiliary controlled diastereoselective aza-Claisen rearrangement. Starting from (S)-configured auxiliaries derived from optically active proline, an aza-Claisen rearrangement enabled us to synthesize a(R)-configured g,d-unsaturated amides. Since (R)-allylglycine derivatives could be directly generated by reacting N-allylproline derivatives and various protected glycine fluorides, the corresponding (S)-enantiomers were built-up via an initial a-chloroacetyl chloride rearrangement and a subsequent chloride azide substitution with complete inversion of the configuration.High diastereoselectivities were obtained ( > 15 : 1). The auxiliary could be efficiently removed by organolithium reactions of the amides furnishing a-amino ketones. Another allyllithium addition allowed us to introduce a second allyl chain with high diastereoselectivity. Final ring closures by means of metatheses using Grubbs (I) catalyst gave raise to the formation of enantiopure phenanthridines and cyclohexenes displaying defined substitution patterns ready for alkaloid total syntheses.

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“…[1] Die außergewçhnlich hohe Reaktivität, vereint mit der Verfügbarkeit praktischer Synthesemethoden, führte zu einer verstärkten Verwendung dieser metallorganischen Verbindungen in der organischen Synthese. [2] Allerdings war die stereoselektive Herstellung von nicht-Heteroatom-stabilisierten sekundären Alkyllithiumverbindungen entgegen einigen Berichten [3] eine schwierige Aufgabe. [4,5] Kürzlich zeigten wir, dass ein I/Li-Austausch für die stereoselektive Herstellung unterschiedlich substituierter Cyclohexyllithiumverbindungen, [6] sowie acyclischer sekundärer Alkyllithiumverbindungen mit einer funktionellen Gruppe (FG = OTBS, Ph; TBS = tert-Butyldimethylsilyl) an einer entfernt liegenden Position, [7] Anwendung finden kann.…”

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Stereoselektive Synthese und Reaktionen von in Position 3 funktionalisierten sekundären Alkyllithiumverbindungen

et al. 2015

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In Position 3 mit einer OTBS-Gruppe funktionalisierte sekundäre Alkyllithiumreagentien kçnnen stereokonvergent durch einen I/Li-Austausch aus einer Diastereomerenmischung der entsprechenden sekundären Alkyliodide hergestellt werden. Diese Lithiumreagentien reagieren mit einer Bandbreite an Elektrophilen, einschließlich Kohlenstoffelektrophilen, unter hoher Retention der Konfiguration und bieten Zugang zu verschiedenen 1,3-difunktionalisierten Derivaten mit guter Diastereoselektivität. Kinetische Studien zeigen, dass die 3-Siloxygruppe die Epimerisierung des Lithium-substituierten Kohlenstoffatoms stark beschleunigt. Diese Methode bietet einen neuen Weg hin zu chiralen offenkettigen Molekülen mit exzellenter Stereoselektivität.

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Clean and convenient procedure for converting primary alkyl iodides and .alpha.,.omega.-diiodoalkanes into the corresponding alkyllithium derivatives by treatment with tert-butyllithium

Cited by 203 publications

References 0 publications

Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

Modular Asymmetric Synthesis of Functionalized Azaspirocycles Based on the Sulfoximine Auxiliary

Synthesis and Derivatization of Substituted (R)‐ and (S)‐ C‐Allylglycines

Stereoselektive Synthese und Reaktionen von in Position 3 funktionalisierten sekundären Alkyllithiumverbindungen

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