Partial Reduction of Nitriles to Aldehydes by Catecholalane (1,3,2-Benzodioxaluminole)

Soon, Jin; Chang, Seok Woo; Kwon, Oh Oun; Kim, Jong Mi

doi:10.1055/s-1996-5364

Cited by 12 publications

(4 citation statements)

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“…In view of the high preference for nucleophiles to add to the carbonyl function of 2 , we next envisioned removal of this interfering group. While the use of conventional reducing agents (LiAlH 4 , DIBAL-H, catecholalane, BH 3 −Me 2 S complex) was of little avail, treatment of 2 with AlH 3 gave the desired β-enaminonitrile 7 in 75% yield (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Our efforts were then directed toward the addition of a variety of nucleophiles to 7 . However, all attempts at condensing the following reagents, employing a wide range of operating conditions, were uniformly unsuccessful: C-centered nucleophiles (allylcopper reagents, allyltrimethylsilane in the presence of TBAF, 1-ethoxyvinylmagnesium bromide, 1-ethoxyvinylcerium dichloride); reducing agents (LiAlH 4 , (EtO) 3 AlLiH, catecholalane, DIBAL-H, NaBH 4 through the 1,3-benzoxathiolium tetrafluoroborate derivative, Et 3 SiH through the N -ethylnitrilium tetrafluoroborate derivative, Raney alloy in AcOH); alkali hydroxides (NaOH, KOH, LiOH). In contrast, a surprising outcome was observed when 7 was subjected to 1-ethoxyvinyllithium: dimer 8 was obtained, albeit in a modest yield of 18%.…”

Section: Resultsmentioning

confidence: 99%

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Crystallographic/Experimental Electron Density Characterizations and Reactions with Nucleophiles of β-Enaminonitriles Possessing a Pyrrolobenzazepine Core

et al. 2004

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In connection with a total synthesis of cephalotaxine (1a), we have examined the addition of various nucleophilic reagents to [ABC] subunits 2 and 7 possessing a pyrrolobenzazepine core. In fact, this reaction implicates invariably the carbonyl group of 2. Regarding the reaction of 7 with nucleophiles, the most striking aspect is the complete lack of reactivity of the enaminonitrile moiety. For instance, the condensation of 7 with methylmagnesium bromide involves exclusively the cleavage of the dioxole ring, yielding regioisomers 9 and 10. With the aim of understanding the unexpected reactivity of 2 and 7 toward nucleophiles, crystallographic studies of 2 and 7 and an experimental electron density determination of 7 were carried out. The marked reactivity of the carbonyl group of 2 was interpreted by invoking the weakness of the amide resonance, due to a pronounced delocalization of the N(9) lone pair over the enaminonitrile moiety. The electron density study of 7 reveals this electron delocalization along the enaminonitrile fragment, highlighted and quantified through the bond geometries, topological indicators, and atomic charges, a phenomenon that is responsible for the failure of the addition of nucleophilic species.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Crystallographic/Experimental Electron Density Characterizations and Reactions with Nucleophiles of β-Enaminonitriles Possessing a Pyrrolobenzazepine Core

et al. 2004

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“…The yields of aldehydes both from aromatic and aliphatic nitriles are in the range of 92-100%. 55 There is no observable dependence on the structure of the nitrile. Even the α,β-unsaturated nitrile, cinnamonitrile, is reduced to the corresponding enal in an essentially quantitative yield (Eq.…”

Section: (43)mentioning

confidence: 99%

“…54 and catecholalane (CA) 55 can converts both aliphatic and aromatic nitriles to the corresponding aldehydes in very high yields. However, it is worthwhile to note that potassium 9-sec-amyl-9-BBNH (K9-s-Am-9-BBNH), 33 sodium 72 and lithium 67 tri(diethylamino)aluminum hydrides (STDEA and LTDEA) achieve the selective conversion of aromatic nitriles to aldehydes in the presence of aliphatic nitriles unattacked (Scheme 16).…”

Section: Conversion Of Nitrile To Aldehyde Diisobutylaluminum Hydridmentioning

confidence: 99%

Thirty Six Years of Research on the Selective Reduction and Hydroboration

Soon¹

2011

Bulletin of the Korean Chemical Society

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thirty six years, the author and his collaborators have developed a variety of reducing and hydroborating agents, and applied them to organic synthesis, which involves the 1,2-reduction of α,β-unsaturated carbonyl compounds, stereoselective reduction of cycloalkanones, regioselective ring-opening of epoxides, partial reduction of carboxylic acid derivatives to aldehydes, regioselective addition to carbon-carbon multiple bonds, etc. by utilizing metal hydrides and the newly-devised the Meerwein-Ponndorf-Verley (MPV) type reagents. Such developments provide a new synthetic methodology making possible valuable selective reductions and hydroborations, not practical previously.

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Formation of Aldehydes and Ketones by Reduction of Phenols, Carboxylic Acids and Deriatives, and Nitriles

Larock

Dubrovskiy

Markina

2018

Comprehensive Organic Transformations

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Phenols and Derivatives Acylsilanes Carboxylic Acids Acid Halides Anhydrides Esters Thioesters Selenoesters Lactones Amides and Imides Nitriles and Acyl Nitriles 4,5‐Dihydrooxazoles and 2‐Imidazolines

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Partial Reduction of Nitriles to Aldehydes by Catecholalane (1,3,2-Benzodioxaluminole)

Cited by 12 publications

References 0 publications

Crystallographic/Experimental Electron Density Characterizations and Reactions with Nucleophiles of β-Enaminonitriles Possessing a Pyrrolobenzazepine Core

Crystallographic/Experimental Electron Density Characterizations and Reactions with Nucleophiles of β-Enaminonitriles Possessing a Pyrrolobenzazepine Core

Thirty Six Years of Research on the Selective Reduction and Hydroboration

Formation of Aldehydes and Ketones by Reduction of Phenols, Carboxylic Acids and Deriatives, and Nitriles

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