Selective reduction of less reactive carbonyl groups in the presence of diborane and sodium bisulfite on silica gel

Teiji Chihara; Tamie Wakabayasi; Kazuo Taya; Haruo Ogawa

doi:10.1139/v90-112

Selective reduction of less reactive carbonyl groups in the presence of diborane and sodium bisulfite on silica gel

Canadian Journal of Chemistry ◽

10.1139/v90-112 ◽

1990 ◽

Vol 68 (5) ◽

pp. 720-724 ◽

Cited By ~ 7

Author(s):

Teiji Chihara ◽

Tamie Wakabayasi ◽

Kazuo Taya ◽

Haruo Ogawa

Keyword(s):

Carbonyl Group ◽

Carbonyl Compound ◽

Silica Gel ◽

Carbonyl Compounds ◽

Selective Reduction ◽

Aromatic Aldehydes ◽

Sodium Bisulfite ◽

Carbonyl Groups ◽

Selective Reaction ◽

Reactive Carbonyl

The less reactive carbonyl group of a mixture of reducible groups of carbonyl compounds was preferentially reduced with diborane on silica gel by first forming an adduct of the more reactive carbonyl group with sodium bisulfite. For example, 4-acetylbenzaldehyde could be converted to 4-(1-hydroxylethyl)benzaldehyde in 93% selectivity; in a mixture of 4-phenyl-acetophenone and 4-phenylbenzaldehyde, biphenylethanol was preferentially formed in 95% yield with 16% yield of 4-phenylbenzyl alcohol. Silica gel and sodium bisulfite were essential for this selective reaction. Aliphatic and aromatic aldehydes and unhindered cyclohexanones could be selectively protected by this method. Keywords: sodium bisulfite, silica gel, carbonyl compound, selective reduction, diborane.

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Reaction of dimethoxycarbene with strained cyclic carbonyl compounds

Canadian Journal of Chemistry ◽

10.1139/v00-118 ◽

2000 ◽

Vol 78 (9) ◽

pp. 1194-1203

Author(s):

Paul C Venneri ◽

John Warkentin

Keyword(s):

Carbonyl Group ◽

Carbonyl Compounds ◽

Ring Expansion ◽

Carbonyl Groups

A cyclopropanone, a cyclopropenone, cyclobutanones, a cyclobutane-1,3-dione, and a cyclobutene-1,2-dione reacted with dimethoxycarbene to afford acetals of the next larger ring by formal insertion of the carbene into a CC bond α to the carbonyl group. When either of two saturated α-ring carbons could be involved in the process, the ring expansion was selective, affording primarily the product of apparent insertion into the more substituted ring bond. With 2,3-dimethoxycyclobutene-1,2-dione, insertion occurred between the carbonyl groups and with β-propiolactone it occurred at the lactone bond. β-Propiolactam, however, reacted by insertion of the carbene into the NH bond.Key words: β-propiolactone, cyclobutanone, cyclobutananedione, cyclopropanone, dialkoxycarbene.

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Reduction by tributyltin hydride of carbonyl compounds adsorbed on silica gel: selective reduction of aldehydes

The Journal of Organic Chemistry ◽

10.1021/jo00414a043 ◽

1978 ◽

Vol 43 (20) ◽

pp. 3977-3979 ◽

Cited By ~ 54

Author(s):

Norman Y. M. Fung ◽

Paul De Mayo ◽

J. Herman Schauble ◽

Alan C. Weedon

Keyword(s):

Silica Gel ◽

Carbonyl Compounds ◽

Selective Reduction ◽

Tributyltin Hydride

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ChemInform Abstract: REDUCTION BY TRIBUTYLTIN HYDRIDE OF CARBONYL COMPOUNDS ADSORBED ON SILICA GEL- SELECTIVE REDUCTION OF ALDEHYDES

Chemischer Informationsdienst ◽

10.1002/chin.197910157 ◽

1979 ◽

Vol 10 (10) ◽

Author(s):

N. Y. M. FUNG ◽

P. MAYO ◽

J. H. SCHAUBLE ◽

A. C. WEEDON

Keyword(s):

Silica Gel ◽

Carbonyl Compounds ◽

Selective Reduction ◽

Tributyltin Hydride

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The mercury-photosensitized decomposition of carbonyl compounds

Proceedings of the Royal Society of London Series A - Mathematical and Physical Sciences ◽

10.1098/rspa.1965.0047 ◽

1965 ◽

Vol 284 (1396) ◽

pp. 1-8 ◽

Cited By ~ 2

Keyword(s):

Carbonyl Group ◽

Carbonyl Compound ◽

Butyric Acid ◽

Carbonyl Compounds ◽

Relative Rate ◽

Vapour Phase ◽

Type I ◽

Type Ii ◽

Propyl Ketone ◽

The Absolute

The mercury-photosensitized and the unsensitized photolyses of n -butyric acid, n -butyraldehyde, and methyl n -propyl ketone have been carried out, and the products analysed by vapour-phase chromatography. These experiments have shown that the primary processes may be of two main types: (I) scission of the bond adjacent to the carbonyl group, and (II) rearrangement to give an olefin and a lower carbonyl compound. In the case of methyl n -propyl ketone, these processes are CH 3 COC 3 H 7 → CH 3 CO´+ C 3 H 7 (type I), and CH 3 COC 3 H 7 → CH 3 COCH 3 + C 2 H 4 (type II). These two processes occur at the same relative rate in both sensitized and unsensitized cases, the absolute rates of the sensitized process being much faster as a result of the greater absorption of radiation. In this latter case, extended photolysis causes the olefinic products formed initially to disappear, as a result of hydrogenation at the expense of higher hydrocarbons formed in the type I reaction. The failure of Borrell & Norrish to detect a photosensitized type II reaction is readily explained by these observations.

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Article

Canadian Journal of Chemistry ◽

10.1139/v98-047 ◽

1998 ◽

Vol 76 (4) ◽

pp. 490-497

Author(s):

Okba Saied ◽

Benoit Bachand ◽

James D Wuest

Keyword(s):

Carbonyl Group ◽

Carbonyl Compounds ◽

Lewis Acids ◽

Carbonyl Oxygen ◽

The Other ◽

Keto Group ◽

Carbonyl Groups ◽

Lone Pairs ◽

Related Compounds ◽

Oxygen Atoms

Carbonyl oxygen atoms have two formal lone pairs of electrons. In principle, both can be used simultaneously to form complexes with two or more Lewis acids. This multiple coordination promises to have a variety of interesting consequences; unfortunately, however, complexes of carbonyl compounds with multiple Lewis acids are extremely rare. To promote multiple coordination, we have made a series of symmetric ketodiesters and related compounds in which the carbonyl group of a ketone is flanked by two additional sites of Lewis basicity. In such compounds, the flanking bases and both lone pairs of the central ketone are available for binding two equivalents of suitable Lewis acids, thereby producing symmetric double chelates in which the central ketone interacts with two Lewis acids at the same time. As expected, treatment of 3-oxoglutarates and 4-oxopimelates with TiCl4 in a 1:1 ratio yielded unsymmetric single chelates in which the carbonyl groups of the ketone and one ester bind TiCl4, while the other ester remains free. Unfortunately, treatment of the same ketodiesters with TiCl4 in a 1:2 ratio did not produce the desired symmetric double chelates. Instead, 2:4 complexes were formed in which the free esters of the unsymmetric single chelates bind TiCl4 in the normal way, without assistance from the keto group. We attribute this observation to the inherent reluctance of ketones to bind multiple Lewis acids, as well as to unfavorable Cl · · ·Cl interactions created in the hypothetical double chelates by the simultaneous attachment of two octahedrally coordinated atoms of titanium to a single carbonyl oxygen atom.Key words: Lewis acids, chelation, ketodiesters, TiCl4.

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ChemInform Abstract: CHEMISTRY OF IRON CARBONYL ANIONS. SELECTIVE REDUCTION OF NITROARENES AND α,β-UNSATURATED CARBONYL COMPOUNDS, AND REDUCTIVE DEHALOGENATION OF ORGANIC HALIDES BY (C2H5)4N+ HFE3(CO)11-

Chemischer Informationsdienst ◽

10.1002/chin.197935298 ◽

1979 ◽

Vol 10 (35) ◽

Author(s):

G. P. BOLDRINI ◽

A. UMANI-RONCHI ◽

M. PANUNZIO

Keyword(s):

Carbonyl Compounds ◽

Selective Reduction ◽

Iron Carbonyl ◽

Reductive Dehalogenation ◽

Organic Halides

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Carbonyl catalysis enables a biomimetic asymmetric Mannich reaction

Science ◽

10.1126/science.aat4210 ◽

2018 ◽

Vol 360 (6396) ◽

pp. 1438-1442 ◽

Cited By ~ 53

Author(s):

Jianfeng Chen ◽

Xing Gong ◽

Jianyu Li ◽

Yingkun Li ◽

Jiguo Ma ◽

...

Keyword(s):

Asymmetric Synthesis ◽

High Activity ◽

Asymmetric Catalysis ◽

Carbonyl Group ◽

Mannich Reaction ◽

Primary Amine ◽

Chiral Amines ◽

Carbonyl Groups ◽

Diphenylphosphinyl Imines

Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a carbonyl group to activate a primary amine. Inspired by biological carbonyl catalysis, which is exemplified by reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst for the asymmetric Mannich reaction of glycinate with aryl N-diphenylphosphinyl imines. The catalyst exhibits high activity and stereoselectivity, likely enabled by enzyme-like cooperative bifunctional activation of the substrates. Our work demonstrates the catalytic utility of the pyridoxal moiety in asymmetric catalysis.

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Copper-Catalyzed Oxidative Self-Coupling of α-Amino Carbonyl Compounds for the Synthesis of Tetrasubstituted 1,4-Enediones

Synlett ◽

10.1055/s-0037-1611227 ◽

2018 ◽

Vol 29 (18) ◽

pp. 2422-2426

Author(s):

Bing Yi ◽

Jiannan Xiang ◽

Niannian Yi ◽

Yi Xiong ◽

Qingjun Huang ◽

...

Keyword(s):

Double Bond ◽

Carbonyl Compound ◽

Carbonyl Compounds ◽

Simultaneous Formation ◽

High Stereoselectivity

A protocol for the copper-catalyzed oxidative self-coupling of α-amino carbonyl compounds has been developed for the synthesis of tetrasubstituted 1,4-enediones (Z-isomers) in moderate to good yields through the cleavage of four sp3C–H bonds and the simultaneous formation of one C=C double bond in the α-amino carbonyl compound. The strategy has the advantages of using readily available starting materials and of high stereoselectivity.

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