Stereoselective synthesis of β-hydroxy substituted trans-alkenes by the reaction of trans-alkenyltrialkylaluminates with epoxides

Negishi, Ei‐ichi; Baba, Shigeru; King, Anthony O.

doi:10.1039/c39760000017

Cited by 48 publications

(35 citation statements)

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“…An isolated publication of the Pd-catalyzed reaction of alkynylsodium [15] should also be noted. Concurrently, Negishi reported the discovery of the Nior Pd-catalyzed cross-coupling reactions of alkenylalanes [16,17].…”

Section: Why Transition Metal-catalyzed Organometallic Reactions?mentioning

confidence: 99%

“…Amidst a series of failures, the Ni-catalyzed Grignard cross-coupling of Tamao et al [10a] was noticed, and a quixotic notion of catalyzing the desired alkenylboron cross-coupling with Ni-phosphine complexes crossed his mind. Although all attempts failed with either alkenylboranes or alkenylborates, they led to the discovery in 1976 of the Ni-catalyzed cross-coupling of alkenylalanes readily accessible by hydroalumination of alkynes (Scheme 3.2) [16,17].…”

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

“…This was when structurally related Pd and Pt complexes were tested. At that time, a survey of (1) (2) HAli Bu 2 Scheme 3.2 First observation of the superior stereoselectivity observed with Pd catalysts relative to that with Ni catalysts [16,17].…”

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

“…Nearly 10 foundation-laying publications by Negishi's group published during the 1976-1978 period [16,17,[21][22][23]29], were further supplemented with a couple of dozen seminal papers on the Pd-or Ni-catalyzed alkylation [35], allylation [28,36], benzylation [22a, 37], and acylation [38] reported during the following decade. In the meantime, many other groups, most notably those led by J.…”

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

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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

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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.

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Section: Why Transition Metal-catalyzed Organometallic Reactions?mentioning

confidence: 99%

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

Section: Discovery Of the Pd-or Ni-catalyzed Cross-coupling Reactionsmentioning

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

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show abstract

“…Negishi and co-workers must be credited with bringing more practical reagents into the menu of the synthetic organic chemist, i.e., Al, Zr and the now very popular Zn derivatives. [6] Indeed, among practitioners, cross-coupling reactions involving organozinc reagents are now referred to as "Negishi couplings".…”

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confidence: 99%

Researchers in This Field Still Have Many Challenges in Front of Them, but the Future is Indeed Very Bright

Farina

2004

Adv Synth Catal

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Oxiranes

Bartók¹,

Lang²

1985

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Stereoselective synthesis of β-hydroxy substituted trans-alkenes by the reaction of trans-alkenyltrialkylaluminates with epoxides

Abstract: Lithium trans-alkenyltrialkylaluminates, prepared by the hydroalumination of alkynes followed by treatment with n-butyl-lithium, react with epoxides to produce P-hydroxy-substituted trans-alkenes, which are readily convertible into py-unsaturated carbonyl derivatives.

Cited by 48 publications

References 0 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

Researchers in This Field Still Have Many Challenges in Front of Them, but the Future is Indeed Very Bright

Oxiranes

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