The reaction of trialkylboranes with diazoacetone. A new ketone synthesis

Hooz, John; Linke, Siegfried

doi:10.1021/ja01023a070

Cited by 113 publications

(26 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[41][42][43] Der postulierte Mechanismus dieser Reaktion (Schema 38) ähnelt den Mechanismen der klassischen Hooz- [45] und Brown-Reaktionen [46] stabilisierter Diazoverbindungen mit Alkylboranen sowie der kürzlich von Wang et al [47] …”

Section: Reduktive Kreuzkupplungen Von Tosylhydrazonen Mit Boronsäurenunclassified

“…Im Verlauf von Untersuchungen der Kreuzkupplungsreaktion von Tosylhydrazonen mit Arylhalogeniden in Ge- genwart verschiedener Metallkatalysatoren wurde die Bildung eines Sulfons 74 beobachtet. [41][42][43] [45] und Brown-Reaktionen [46] stabilisierter Diazoverbindungen mit Alkylboranen sowie der kürzlich von Wang et al [47]…”

Section: Reduktive Kreuzkupplungen Von Tosylhydrazonen Mit Boronsäurenunclassified

See 1 more Smart Citation

Tosylhydrazone – neue Anwendungen klassischer Reagentien in palladiumkatalysierten Kreuzkupplungen und metallfreien Umsetzungen

2011

View full text Add to dashboard Cite

Tosylhydrazone sind wertvolle Zwischenverbindungen, die in der organischen Chemie seit fast 60 Jahren Anwendung finden. Die jüngste Entdeckung einer palladiumkatalysierten Kreuzkupplungsreaktion unter Beteiligung eines Tosylhydrazon‐Kupplungspartners weckte ein neues Interesse an diesen Reagentien. Die Reaktion ist nahezu universell für Hydrazone und kann zur Synthese polysubstituierter Alkene genutzt werden. Im Verlauf dieser Forschungen wurden außerdem neue metallfreie C‐C‐ und C‐O‐Kupplungen gefunden. Da Tosylhydrazone leicht aus Carbonylverbindungen zugänglich sind, bieten diese Umwandlungen neue Möglichkeiten für die Derivatisierung von Carbonylverbindungen. Dieser Kurzaufsatz behandelt diese neuartigen Reaktionen dieses klassischen Reagens.

show abstract

Section: Reduktive Kreuzkupplungen Von Tosylhydrazonen Mit Boronsäurenunclassified

Tosylhydrazone – neue Anwendungen klassischer Reagentien in palladiumkatalysierten Kreuzkupplungen und metallfreien Umsetzungen

2011

View full text Add to dashboard Cite

show abstract

“…Tri-n-butylborane gave almost exclusively the (E)-enolate, which could be isomerized quantitatively to the (Z)-enolate by a catalytic amount of pyridine or lithium phenoxide (Scheme 24). 82 This method has the disadvantage that only one of the three alkyl groups is utilized. If boranes with different substituents are employed, the question arises as to which substituent has the highest 'migration aptitude'.…”

Section: Boron Enolatesmentioning

confidence: 99%

2.06 Formation of Enolates

Mekelburger

Wilcox

2014

Comprehensive Organic Synthesis II

View full text Add to dashboard Cite

“…The discovery of the oxidative addition of standing of their oxidative addition reactions simple covalent molecules to transition metal would help to solve one of the outstanding complexes has led to major advances in the field problems in homogeneous catalysis, namely, the of homogeneous catalysis (1,2). Our interest has activation of saturated hydrocarbons.…”

Section: Conversions Of Olefins Into Aldehydesmentioning

confidence: 99%

“…The only definitive reaction mechanism that has thus far been demonstrated for oxidative addition to a five-coordinate d8 complex is that shown in reactions [2] and [3], according to Collman and Roper (1) [21 o c + co + l2 -lo*]:-…”

Section: Conversions Of Olefins Into Aldehydesmentioning

confidence: 99%

Reaction of trialkylboranes with diazoacetaldehyde. A new synthesis of aldehydes

Hooz¹,

Morrison²

1970

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

A new aldehyde synthesis has been developed, based on the reaction of organoboranes with diazoacetaldehyde.Canadian Journal of Chemistry, 48, 868 (1970) Previous publications have described syntheses ized and homologated. We have expanded this of ketones (I), nitriles (2), esters (2), and diketones versatile method to include a new, mild aldehyde (3), in which olefins, via their organoborane synthesis which permits a 2-carbon-atom extenderivatives, have been simultaneously functional-sion (ethanaiation) of olefins by the reaction of Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.201.150.21 on 05/10/18For personal use only. This process conveniently augments the repertory of organoborane-based aldehyde syntheses, which to date have been limited to 1-(4) and 3-carbon-atom (5) chain-lengthening reactions.Some typical examples are summarized in Table 1. The reactions of organoboranes derived from 1-alkenes as well as cyclopentene proceed in good yield (77-98 %); yields are lower, however, for sterically-hindered trialkylboranes. Triarylboranes also react successfully, as exemplified by the conversion of triphenylborane to phenylacetaldehyde (76 %).Although the hydroboration of monosubstituted terminal olefins produces approximately 94 % primary and 6 % secondary alkyl groups (6), the product from reaction of the trialkylborane derived from I-butene was hexanal; no evidence (gas-liquid phase chromatography (g.1.p.c.)) for the formation of 3-methylpentanal was observed. Since a similar migrational preference of primary over secondary alkyl groups has also been noted in the organoborane-diazoacetic ester reaction (2), these developments permit the synthesis of functional derivatives free of isomeric contaminants. By way of contrast, the 3-carbon aldehyde homologation, involving reaction of trialkylboranes with acrolein (5), gives products derived from preferential migration of the secondary alkyl groups in the organoborane. ' Functional diazo substrates react with organoboranes to produce intermediates which undergo hydrolysis with extreme ease (2). The g.1.p.c. analysis of a crude tributylborane-diazoacetaldehyde reaction mixture after complete consumption of diazo compound, but prior to the addition of water, revealed the presence of some hexanal. The infrared (i.r.) spectrum exhibited absorption at 1730 (aldehyde carbonyl) and 1670 cm-' (en01 ether ?); the latter disappeared at the 'A limitation of the R3B-diazo reaction at present, a difficulty also encountered in the propanalation process, is that but one alkyl moiety is utilized. Although B-alkyl-9-borabicyclo [3.3.1 Inonane (B-R-9-BBN) derivatives have recently been very effectively employed to circumvent this difficulty in the carbonylation reaction and the alkylation of x-halocarbanions (7), diazo substrates react with B-R-9-BBN derivatives with preferential B-cyclooctyl bond migration (8, 9).However, B-R-9-BBN derivatives fail to react with acrolein. expense of the former after addition of water. This observation is highly reminiscent of th...

show abstract

The reaction of trialkylboranes with diazoacetone. A new ketone synthesis

Abstract: 10) Analogous proposals have appeared to account for the reactions of trialkylboranes with ylides1 and carbanions.2 See also ref 3.

Cited by 113 publications

References 1 publication

Tosylhydrazone – neue Anwendungen klassischer Reagentien in palladiumkatalysierten Kreuzkupplungen und metallfreien Umsetzungen

Tosylhydrazone – neue Anwendungen klassischer Reagentien in palladiumkatalysierten Kreuzkupplungen und metallfreien Umsetzungen

2.06 Formation of Enolates

Reaction of trialkylboranes with diazoacetaldehyde. A new synthesis of aldehydes

Contact Info

Product

Resources

About