Reduction of organic halogen compounds by sodium borohydride

Bell, Harold M.; Vanderslice, C. Warren; Spehar, Andrea

doi:10.1021/jo01264a038

Cited by 110 publications

(27 citation statements)

References 1 publication

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“…After being stirred at this temperature for 9 h, the mixture was directly subjected to column chromatography on silica gel (2 g) using a 1O:l mixture of hexane and ether as eluant to give 50 (19.6 mg, 95%): TLC R 0.57 (1:l etherfhexane); 'H NMR (CDCl,) 6 2.C-2.7 (m, 4, 2 Cd2), 3.32 (s,8 ,4 CHZ) 2,2 CHO), 7.2-7.7 (m, 10, Ar); ' 9 NMR (CDClJ 6 26. 3,57.2,57.9,125.1,127.7,128.5,140.5;MS,mfz 264 (M+). Anal.…”

Section: Conversion Of 25 To the Diepoxide 64 And The Furan 65 (Entrymentioning

confidence: 99%

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Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation

Mock¹,

Irra²,

Wepsiec³

et al. 1989

J. Org. Chem.

275

366

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Chemical Research (RIKEN) for donation of rutheniumcatalysts. We are also indebted to Professor S. Suzuki of our department for the suggestion for the malonaldehyde assay. We also thank Professor K. Hirao of our University for his helpful guidance in conducting MO calculations.A mechanistic investigation is described for the cycloaddition induced between RNH2+CH2C=CH and RNHz+CH2CHzN3 (R = H, t-Bu) consequent to encapsulation by the polycyclic molecular receptor cucurbituril (C3BH9sNU012). The reaction is shown to be substantially accelerated (ca. lo5-fold), and the kinetic characteristics of catalytic saturation behavior, substrate inhibition, and slow product release are documented. For substrates with R = t-Bu a rotaxane product results, and inhibition kinetics with NH3+CH2CH2C(CH3), are also examined. A rate enhancement attributed to bound-substrate destabilization is detected. The significance of this effect and its connection with the phenomenon of nonproductive binding in catalytic systems are discussed.Understanding enzymic catalysis represents perhaps the most severe challenge of mechanistic organic chemistry. Because of the complexity of proteins, analogues which mimic aspects of biochemical catalysis are desirable. Excellent progress has been made in devising synthetic molecular receptors, and much is being learned about spe-(1). Taken in part from the Ph.D. Thesis of M. Adhya, University of Illinois, Chicago, 1986; Diss. Abstr. Int. B 1986, 47, 1056. 0022-3263/89/1954-5302$01.50/0 0 cificity in molecular recognition from imaginatively engineered models of this naturee2 Even more arduous is (2) Recent reviews: Brealow, R. Adv. Enzymol. Relat. Areas Mol. Biol. 1986, 58, 1. Franke, J.; Vogtle, T. Top. Curr. Chem. 1986, 132, 135. Sutherland, I. 0. Chem. SOC. Rev. 1986, 15, 63. Cram, D. J. Angew,

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Section: Conversion Of 25 To the Diepoxide 64 And The Furan 65 (Entrymentioning

confidence: 99%

“…LC: SiOz (5 g), hexane/ether (5:l) as the eluant. 66: 'H NMR (CDC13) 6 1.23 (s, 3,CHd,1.30 (s,3,CH,), 1.6-1.9 (m, 2, CH2), 2.4-2.9 (m, 3, CHO and CH2), 6.30 (br s, 1, Ar), 2,Ar).4f…”

Section: Conversion Of Ascaridolementioning

confidence: 99%

Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation

Mock¹,

Irra²,

Wepsiec³

et al. 1989

J. Org. Chem.

275

366

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“…A deuterium incorporation of 95 % was obtained by adaptation of a technique reported for 2-deuterionitrobenzene. [14] With this elegant method, the iodo substituent of 3-iodo-2-nitroanisole is replaced by deuterium on reduction with sodium borohydride in D 2 O/diglyme.…”

Section: Resultsmentioning

confidence: 99%

“…[27] Deuteriated compound [D]7 was prepared by reductive deuteriation of the iodobenzene derivative. [14] To a stirred mixture of diglyme (14 mL) and D 2 O (4 mL) was added a solution of 1-iodo-3-methoxy-2-nitrobenzene (560 mg, 2 mmol) in diglyme (2 mL) followed by sodium borohydride (150 mg, 4 mmol). After stirring for 90 min, the reaction mixture was decomposed by HCl (1 m) and extracted with light petroleum (5 ϫ 20 mL).…”

Section: -Deuterio-2-nitroanisole ([D]7)mentioning

confidence: 99%

The Mechanism of the ortho‐Methylation of Nitrobenzenes by Dimethylsulfonium Methylide

Haiß

Zeller

2010

Eur J Org Chem

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Nitrobenzenes carrying an ortho substituent are selectively methylated at the free ortho position by reaction with dimethylsulfonium methylide. The importance of the ortho substituent is demonstrated by the failure of the methylation of nitrobenzene and 3-and 4-nitroanisole. This is explained by the out-of-plane geometry of the nitro group in the orthosubstituted derivative, which enables a specific interaction

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“…Reduction of the bromide, accomplished by sodium borohydride in dimethyl sulphoxide (26,27) gave, in 95% yield, the a,P-unsaturated nitrile 43 and the non-conjugated nitrile 44, as a 90: 10 mixture.…”

Section: C1 CImentioning

confidence: 99%

The chemistry of thujone. XVI. Versatile and efficient routes to safronitrile, β-cyclogeranonitrile, β-cyclocitral, damascones, and their analogues

Kutney¹,

Gunning²,

Clewley³

et al. 1992

Can. J. Chem.

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. Thujone, a waste by-product of the Canadian forest industry, has been utilized as a starting material to develop a versatile synthetic route to the darnascones (rose oil ketones) and related analogues. The synthetic sequence provides a route to P-cyclocitral ( 4 9 , the latter having been previously converted to P-damascone (2). In addition, thujone-derived intermediates are converted to P-damascenone (48) and to intermediates that can be utilized for the preparation of damascone analogues. In conjunction with the above, an efficient route to safronitrile (42), P-cyclogeranonitrile (43), and P-cyclocitral (45) from 2,6-dimethylcyclohexanone has been developed. In summary, these studies afford an attractive versatile route to these important perfumery materials.

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Reduction of organic halogen compounds by sodium borohydride

Cited by 110 publications

References 1 publication

Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation

Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation

The Mechanism of the ortho‐Methylation of Nitrobenzenes by Dimethylsulfonium Methylide

The chemistry of thujone. XVI. Versatile and efficient routes to safronitrile, β-cyclogeranonitrile, β-cyclocitral, damascones, and their analogues

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