Cobalt- and rhodium-catalyzed cross-coupling reaction of allylic ethers and halides with organometallic reagents

Yasui, Hiroto; Mizutani, Keiya; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1016/j.tet.2005.11.032

Cited by 65 publications

(36 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…19 To the best of our knowledge, α-selective cobalt-catalyzed allylic substitutions with organometallic reagents have proven successful to date only with diarylzinc compounds on allylic chlorides, 20 and when Grignard reagents were coupled with allylic ether substrates. 13 This latter reaction demonstrated high dependency on the structure of the substrate, ligand, and Gignard reagent used. In addition, moderate regioselectivity was observed (competition of α-selectivity vs γ-selectivity 19 ) as well as C=C bond migration on some substrates, to give mixtures of three different products.…”

mentioning

confidence: 99%

Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand

et al. 2015

View full text Add to dashboard Cite

Sarcosine was discovered to be an excellent ligand for cobalt-catalyzed carbon-carbon cross-coupling of Grignard reagents with allylic and vinylic bromides. The Co(II)/sarcosine catalytic system is shown to perform efficiently when phenyl and benzyl Grignards are coupled with alkenyl bromides. Notably, previously unachievable Co-catalyzed coupling of allylic bromides with Grignards to linearly coupled α-products was also realized with Co(II)/sarcosine catalyst. This method was used for efficient preparation of the key intermediate in an alternative synthesis of the antihyperglycemic drug sitagliptin.

show abstract

mentioning

confidence: 99%

Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Although cobalt salts can catalyze the cross-coupling of arylmagnesium reagents with activated electrophiles such as heterocyclic chlorides [87] or allylic ethers [88], their main importance is their use in the cross-coupling of alkenyl Grignard derivatives with alkenyl triflates [89]. The formation of the trisubstituted 1,3-diene 125 using a combination of Co(acac) 3 and PPh 3 as the catalytic system is a representative example of such a coupling.…”

Section: Cobalt-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

“…It is of interest that not only primary, but also secondary and tertiary alkyl halides can be used. Furthermore, a similar catalytic system involving 1,6-bis(diphenylphosphinohexane) is competent to promote the coupling of (trimethylsilylmethyl)magnesium chloride with allylic ethers [88].…”

Section: Cross-coupling With C(sp 3 )-Electrophilesmentioning

confidence: 99%

Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Chemla

Ferreira

Pérez‐Luna

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

View full text Add to dashboard Cite

IntroductionFirst reported at the beginning of the twentieth century [1], organomagnesiums are very important synthetic tools. In the field of coupling reactions, first examples of transition-metal-mediated reactions have been reported by Gilman and Lichtenwalter [2] with the oxidative homo-coupling of aryl Grignard reagents in the presence of transition metal halides as both catalyst precursors and oxidants. This reaction was later greatly improved by Kharasch [3], who showed that an efficient homo-coupling reaction could be observed with a small amount of CoCl 2 (3 mol%) and an organic halide as a stoichiometric oxidant. This breakthrough was then followed by the report in 1941 on cross-coupling reactions of arylmagnesium bromides with vinylic halides in the presence of various transition metal salts by the same group [4]. Surprisingly, this seminal work remained mainly unexploited, until this reaction was reinvestigated by several groups in the beginning of the 1970s [5]. Thus, Kochi and Tamura [6, 7] described in 1971 the use of Fe(III) salts as catalyst precursors for cross-coupling reactions, while Kumada [8] and Corriu [9] reported the use of nickel for similar transformations [10,11]. At the same time, the group of Normant [12] described the Cu-catalyzed reaction of the Grignard reagents with organic halides, followed by the report of Murahashi [13] on the use of palladium as a catalyst in similar cross-couplings. Most cross-coupling reactions have been performed with unfunctionalized Grignard reagents because no general method for preparing oligofunctional organomagnesium reagents was available. However, the situation is rapidly evolving, thanks to the groundbreaking work of Knochel and coworkers [14] on the preparation of highly functionalized Grignard reagents. In this chapter, the scope and limitations of cross-coupling reactions involving organomagnesium reagents are showcased with select examples from the recent literature with a special focus on functional-group-tolerant procedures. The recent developments of the most challenging transformations including either the use of oligofunctional metallic species or β-hydrogen-containing nucleophiles will be specially highlighted.

show abstract

“…[10] This methodology accommodates a wide range of carbon nucleophiles, such as activated methylene compounds, [11] enolates, [12] enamines, [13] Grignard reagents, [14] organozinc reagents [15] and alkenyl [16] or aryl [17] boron reagents. ASR of terminal alkenes, in principle, would enable the construction of 1,4-dienes ("skipped" dienes), a key structural motif prevalent in natural products.…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Allylic Substitution of Simple Alkenes

Matsubara

Jamison

2010

Synfacts

View full text Add to dashboard Cite

This report describes a nickel-catalyzed allylic substitution process of simple alkenes whereby an important structural motif, a 1,4-diene, was prepared. A key for this success is the use of an appropriate Ni-phosphine complex and a stoichiometric amount of silyl triflate. Reactions of 1-alkyl-substituted alkenes consistently provided 1,1-disubstituted alkenes with high selectivity. Insight into the reaction mechanism as well as miscellaneous application of the developed catalytic process is also documented.

show abstract

Cobalt- and rhodium-catalyzed cross-coupling reaction of allylic ethers and halides with organometallic reagents

Cited by 65 publications

References 21 publications

Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand

Cobalt-Catalyzed Cross-Coupling of Grignards with Allylic and Vinylic Bromides: Use of Sarcosine as a Natural Ligand

Carbon–Carbon‐Bond‐Forming Reactions Mediated by Organomagnesium Reagents

Nickel-Catalyzed Allylic Substitution of Simple Alkenes

Contact Info

Product

Resources

About