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

Anastasia, Luigi; Dumond, Yves; Negishi, E.

doi:10.1002/1099-0690(200108)2001:16<3039::aid-ejoc3039>3.0.co;2-v

Cited by 28 publications

(13 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To a mixture of Mg turnings (0.9 g, 36.8 mmol), I 2 (one crystal), and CH 2 Br 2 (20 μl) in THF (2 ml) was added a solution of commercially available 5-bromo-2-methyl-2-pentene (3 g, 18.4 mmol) and anhydrous ZnBr 2 (4.4 g, 19.6 mmol) dissolved in THF (20 ml) (Scheme 3.35) [74]. The reaction mixture was heated to gentle reflux for 7 h. In another flask, a solution of (Z)-2-(1-iodoethylidene)pent-4-en-1-ol (2.9 g, 12.3 mmol, prepared by Cu-catalyzed allylmagnesiation of 2-butyn-1-ol) in THF (30 ml) was added dropwise to a solution of EtMgBr (1 M in THF, 12.28 ml) and…”

Section: (2z)-2-allyl-37-dimethylocta-26-dien-1-olmentioning

confidence: 94%

“…Duboudin's Cu-catalyzed anti carbomagnesiation of propargyl alcohol derivatives is one of still a small number of currently known carbometallation reactions of very high (≥98%) regio-and stereoselectivity (Scheme 3.13b), which can be profitably exploited, as exemplified by the efficient and highly selective synthesis of both (E)-and (Z)-γ-bisabolenes (Scheme 3.35) [74]. It does appear reasonably certain that, as long as the requisite Types IX and X alkenyl reagents can be obtained in the y(es) 2 manner, Pd-catalyzed alkenylation, especially by the Negishi version, will provide a wide range of tetrasubstituted alkenes of defined regio-and stereochemistry.…”

Section: Tetrasubstituted Alkenes Via Types IX and X Alkenyl Reagentsmentioning

confidence: 99%

“…), (ii) CO 2 Scheme 3.33 Syntheses of the side chain of mycolactone A and lissoclinolide by Pd-catalyzed Negishi alkenylation of 1,1-dibromoalkenes.Scheme 3.34Pd-catalyzed Negishi alkenyl-alkenyl coupling used in the synthesis of (+)-carbacyclin[148]. Scheme 3.35 Stereoselective (≥98%) syntheses of (E)-and (Z)-γ-bisabolenes by Pdcatalyzed Negishi alkenyl-alkenyl coupling[74].…”

mentioning

confidence: 99%

See 2 more Smart Citations

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

Kamada

Kim

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

Self Cite

View full text Add to dashboard Cite

The Pd-or Ni-catalyzed cross-coupling reactions of organometals containing Zn, Al, Zr, and B as well as related reactions of those containing Mg and several other metals collectively have emerged as arguably the most widely applicable organic skeleton construction method discovered and developed over the past several decades, allowing synthetic chemists to prepare practically all types of organic compounds. In this chapter, some of the seminal and critically important discoveries and early developments in the 1970s as well as their current scope are briefly discussed. Some of the notable discoveries and developments include (i) identification of superior properties of Pd as a critical element for crosscoupling relative to Ni, (ii) the broad scope of Pd-or Ni-catalyzed cross-coupling with respect to metal countercations including Zn, Al, Zr, B, and Mg, (iii) the hydrometallation-Pd-catalyzed cross-coupling sequential processes for selective syntheses of alkenes, dienes, oligoenes, and oligoenynes, (iv) double metal catalysis involving Pd or Ni and added metal compounds containing Zn, In, Li, and others, and (v) realization of high turnover numbers (TONs) (≥10 3 -10 9 ) through the use of chelating phosphines, such as bis-[2-(diphenylphosphino)phenyl] ether (DPEphos) and 1,1 -Bis(diphenylphosphino)ferrocene (dppf).The Zr-catalyzed alkyne carboalumination and the Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction) have provided efficient and selective routes to (E)-trisubstituted alkenylalanes and 2-substituted chiral alkylalanes, respectively. These reactions provide two additional examples of prototypical transition metal-catalyzed organometallic reactions. Significantly, they can be readily combined with the Pd-or Ni-catalyzed cross-coupling for the synthesis of trisubstituted alkenes embracing a wide variety of natural products, such as terpenoids, carotenoids, and others, as well as various chiral organics including deoxypolypropionates and saturated terpenoids. The Zr-catalyzed alkyne carboalumination has been applied to the synthesis of a large number (>100) of natural products, while the ZACA reaction has been transformed from a mere scientific novelty to a full-fledged asymmetric synthetic method that is catalytic in both transition metal (Zr) and chiral auxiliaries through a series of breakthroughs.

show abstract

Section: (2z)-2-allyl-37-dimethylocta-26-dien-1-olmentioning

confidence: 94%

Section: Tetrasubstituted Alkenes Via Types IX and X Alkenyl Reagentsmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

Kamada

Kim

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

Self Cite

View full text Add to dashboard Cite

show abstract

“…17 Eqn (3) shows the exceptional but highly important case of primary propargylic alcohol which undergoes unexpected trans allyl-addition to provide the branched product 5 (eqn (3)). 18 However, when the propargylic alcohol is transformed into a leaving group (OLG, e.g. OAc) then propargylic displacement is usually obtained providing the corresponding allene 6 (eqn (4)).…”

Section: Short Overview Of the Carbocupration Reactions Of Alkynesmentioning

confidence: 99%

Copper mediated carbometalation reactions

2016

View full text Add to dashboard Cite

show abstract

“…The trend is the same in copper-catalyzed reactions of wide scope [62]. In 2001, Negishi applied copper-catalyzed allylmagnesiation to the total synthesis of ( Z )-γ-bisabolene (Scheme 6) [63]. …”

Section: Reviewmentioning

confidence: 99%

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Murakami¹,

Yorimitsu²

2013

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryCarbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1) alkynes bearing an electron-withdrawing group; (2) alkynes bearing a directing group; (3) strained cyclopropenes; (4) unactivated alkynes or alkenes; and (5) substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes).

show abstract

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

Abstract: Highly efficient stereoselective syntheses of both (Z)-and (E)-γ-bisabolenes (1) were achieved by ring closing metathesis of stereodefined tetrasubstituted alkenes. Both (Z)-and (E)-tetrasubstituted alkene precursors were obtained by Cu-catalyzed stereoselective addition of allylmagnesium

Cited by 28 publications

References 8 publications

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

Pd‐Catalyzed Cross‐Coupling with Organometals Containing Zn, Al, Zr, and so on – The Negishi Coupling and Its Recent Advances

Copper mediated carbometalation reactions

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Contact Info

Product

Resources

About