Highly stereoselective and general synthesis of (z)-3-methyl-2-alken-1-ols via palladium-catalyzed cross coupling of (z)-3-iodo-2-buten-1-ol with organozincs and other organometals

Negishi, Ei‐ichi; Benson, Tom; Gulevich, Yuri; Noda, Y.

doi:10.1016/s0040-4039(00)60312-x

Cited by 78 publications

(21 citation statements)

References 29 publications

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“…Indeed, we earlier demonstrated the feasibility of using EtZnBr as a sacrificial alkylzinc reagent. [20] Rather than improve the synthesis of (Z)-γ-bisabolene shown in Scheme 2, we chose to synthesize the E isomer 1b to demonstrate the practical applicability of the above-mentioned strategy for providing an ultimately satisfactory and selective route to γ-bisabolenes and other related exocyclic alkenes in general.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of Exocyclic Alkenes by Cu-Catalyzed Allylmagnesiation, Pd-Catalyzed Alkylation, and Ru-Catalyzed Ring-Closing Metathesis: Highly Stereoselective Synthesis of (Z)- and (E)-γ-Bisabolenes

2001

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Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of Exocyclic Alkenes by Cu-Catalyzed Allylmagnesiation, Pd-Catalyzed Alkylation, and Ru-Catalyzed Ring-Closing Metathesis: Highly Stereoselective Synthesis of (Z)- and (E)-γ-Bisabolenes

2001

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“…Yields refer to isolated compounds of greater than 95% purity, as estimated by GLC, and 1 H NMR. All compounds were characterized by 1 H NMR, 13 C NMR and mass spectrometry. 1 H NMR and 13 C NMR spectra were recorded on a Bruker Avance AC300 spectrometer operating at 300.213 and 75.44 MHz, respectively.…”

Section: General Methodsmentioning

confidence: 99%

Asymmetric catalysis in fragrance chemistry: a new synthetic approach to enantiopure Phenoxanol®, Citralis® and Citralis Nitrile®

Matteoli¹,

Ciappa²,

Bovo³

et al. 2007

Tetrahedron: Asymmetry

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“…Other natural products synthesized via the Pdcatalyzed alkylation with alkylzincs include casbene [76] (Scheme 1-23) and ageline A [77] (Scheme 1-24). (Q-3-Iodo-2-alken-1 -oh, readily obtainable from propargyl alcohols via either reduction with LiAlH, and related reagents [78] or Cu-catalyzed carbomagnesiation [79] can be cleanly alkylated with alkylzinc derivatives in the presence of Pd-phosphine catalysts [80,81] (Scheme 1-25). The use of LiCu(n-Bu), or a-BuLi without catalysts was unsatisfactory.…”

Section: Palladium-catalyzed Cross-coupling Involving Alkyl Groups Wimentioning

confidence: 99%

Palladium‐ or Nickel‐Catalyzed Cross‐Coupling with Organometals Containing Zinc, Magnesium, Aluminum, and Zirconium

Negishi¹,

Liu²

1998

Metal‐Catalyzed Cross‐Coupling Reactions

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The cross-coupling reaction of organometallic reagents with organic halides and related electrophiles represents one of the most straightforward methods for carbon-carbon bond formation (Scheme 1-1). Despite its inherent simplicity and significance, however, its synthetic utility was very limited until the mid-1960s. Mainly Grignard reagents and organolithiums were used in earlier examples. In such cases, organic halides are mostly limited to alkyl (C,3) halides. Furthermore, the use of organometals containing Mg and Li is often complicated and limited by their generally low chemoselectivity. Although advances in organocopper chemistry [l] over the past three decades have solved many of the difficulties associated with the use of Grignard reagents and organolithiums, a number of other problems have remained unsolved.In 1972, Kumada [2] and Corriu [3] independently reported that the reaction of Grignard reagents with alkenyl or aryl halides could be markedly catalyzed by Ni-phosphine complexes, e.g., Cl,Ni(PPh,),. Although many other transition-metal-catalyzed reactions of Grignard reagents with organic halides without the use of phosphines were known, the socalled Kharasch-type reactions [4], with the exception of the Cu-catalyzed procedures [5,6], were not well suited for cross-coupling due to various complications, including extensive cross-homo scrambling.The discovery of Pd-catalyzed cross-coupling was somewhat more subtle and evolutionary. During the 1975-1976 period, several groups of workers including the present authors' group published various results involving Pd-phosphine complexes. Thus, Cassar "71 reported the Pd-catalyzed cross-coupling reaction of aryl bromides and iodides with sodium acetylides generated in situ by mixing terminal alkynes with NaOMe in DMF (Scheme 1-2). The corresponding reaction using a Ni-phosphine complex did not proceed Catalytically. Similar reactions of alkynes, where the countercations in active species were most probably ammonium and/or Cu', were also reported by Heck [8] and Sonogashira [9] (Scheme 1-2).

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Highly stereoselective and general synthesis of (z)-3-methyl-2-alken-1-ols via palladium-catalyzed cross coupling of (z)-3-iodo-2-buten-1-ol with organozincs and other organometals

Cited by 78 publications

References 29 publications

Stereoselective Synthesis of Exocyclic Alkenes by Cu-Catalyzed Allylmagnesiation, Pd-Catalyzed Alkylation, and Ru-Catalyzed Ring-Closing Metathesis: Highly Stereoselective Synthesis of (Z)- and (E)-γ-Bisabolenes

Stereoselective Synthesis of Exocyclic Alkenes by Cu-Catalyzed Allylmagnesiation, Pd-Catalyzed Alkylation, and Ru-Catalyzed Ring-Closing Metathesis: Highly Stereoselective Synthesis of (Z)- and (E)-γ-Bisabolenes

Asymmetric catalysis in fragrance chemistry: a new synthetic approach to enantiopure Phenoxanol®, Citralis® and Citralis Nitrile®

Palladium‐ or Nickel‐Catalyzed Cross‐Coupling with Organometals Containing Zinc, Magnesium, Aluminum, and Zirconium

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