A New Stereoselective Method for the Preparation of Allylic Alcohols

Oblinger, Eric; Montgomery, John

doi:10.1021/ja9719182

Cited by 260 publications

(115 citation statements)

References 30 publications

Supporting

Mentioning

109

Contrasting

Unclassified

Order By: Relevance

“…13 Step 2: To a 50 mL round-bottomed flask, added 1-(4-nitrophenyl)non-2-yn-1-ol (784 mg, 3.0 mmol), Lindlar catalyst (5% Pd on CaCO 3 , poisoned with Pb, 30 mg), and EtOAc (30 mL). Evacuated flask (aspirator vacuum) and placed under a H 2 atmosphere, stirring at 1000 rpm at room temperature.…”

Section: S4mentioning

confidence: 99%

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

2006

View full text Add to dashboard Cite

The scope of the triphenylsilyl perrhennate (O3ReOSiPh3, 1) catalyzed 1,3-isomerization of allylic alcohols has been thoroughly explored. It was found to be effective for a wide variety of secondary and tertiary allylic alcohol substrates bearing aryl, alkyl, and cyano substituents. Two general reaction types were found which gave high levels of product selectivity: those driven by formation of an extended conjugated system and those driven by selective silylation of a particular isomer. The efficiency of chirality transfer with various substrates was investigated, and conditions were found in which secondary and tertiary allylic alcohols could be formed with high levels of enantioselectivity. Consideration of selectivity trends with respect to the nature of the substituents around the allylic system revealed that this is a reliable and predictable method for allylic alcohol synthesis.

show abstract

Section: S4mentioning

confidence: 99%

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

2006

View full text Add to dashboard Cite

show abstract

“…1997 stellten Montgomery und Oblinger die Synthese von Allylalkoholen aus Alkinen und Aldehyden mit Nickel(0)-Katalysatoren vor (5 Mol-%; Schema 15). [73] Nach Bildung eines Oxanickelacyclus, ähnlich zur oxidativen Kupplung von CO 2 und Olefinen, wird die Ni-O-Bindung durch Diorganozinkverbindungen gespalten, die eine Gruppe R auf das Nickelzentrum transferieren, während die RZn-Gruppe an das Sauerstoffatom bindet (Schema 15). Das Produkt wird durch reduktive Eliminierung abgespalten und der Nickelkatalysator wiedergewonnen.…”

Section: Katalysierte Synthese Von Carbonsäuren Aus Olefinen Und Co 2unclassified

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

et al. 2011

View full text Add to dashboard Cite

In der Vergangenheit wurde eine Vielzahl von Methoden zur Verwendung von Kohlendioxid in der organischen Synthese entwickelt. Trotz der breiten Gesamtverfügbarkeit von CO2 auf der Erde ist sein Einsatz als Reaktant, insbesondere in der Synthesechemie, recht selten. In den letzten 35 Jahren wurde intensiv daran geforscht, kosten‐ und energieeffiziente katalytische Prozesse zu finden, um CO2 zu Carbonsäuren, Estern, Lactonen und Polymeren umzusetzen. Dieser Aufsatz fasst die bis heute vorhandenen homogenkatalytischen Routen zur Verwendung von CO2 als C1‐Kohlenstoffquelle für die Synthese industrieller Produkte sowie Feinchemikalien zusammen.

show abstract

“…In this transformation, diethylzinc served as the stoichiometric reducing agent, while the catalyst was composed of bis(1,5-cyclooctadiene)nickel(0) (Ni(cod) 2 ) and tributylphosphine (eq 2). 11 The authors observed that, in the absence of a catalytic phosphine additive, the alkylative cyclization product (i.e., transfer of Et instead of H from diethylzinc) is observed (eq 3). 11 These cyclization strategies have been further developed and found several applications in total synthesis.…”

Section: 2a) Intramolecular Nickel-catalysed Reductive and Alkylatimentioning

confidence: 99%

“…11 To achieve intermolecular reductive coupling, our group examined a variety of reducing agents and catalytic ligand additives, eventually determining that use of triethylborane in the presence of catalytic Ni(cod) 2 and tributylphosphine provided the E-trisubstituted allylic alcohol with excellent yield and selectivity (eq 5). 13,14 We later found that a similar transformation was also possible using epoxides as coupling partners, which afforded homoallylic alcohol products (eq 6).…”

Section: 2b) Intermolecular Nickel-catalysed Reductive and Alkylatimentioning

confidence: 99%

Regioselectivity and enantioselectivity in nickel-catalysed reductive coupling reactions of alkynes

2007

View full text Add to dashboard Cite

Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included.

show abstract

A New Stereoselective Method for the Preparation of Allylic Alcohols

Cited by 260 publications

References 30 publications

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

Regioselectivity and enantioselectivity in nickel-catalysed reductive coupling reactions of alkynes

Contact Info

Product

Resources

About