13 0 obj /CreationDate (D:20100105163037+01'00') reactions of α,β-unsaturated aldehydes with 1,3-dienes. We thank DST and CSIR, India for financial support and DST-FIST for providing NMR facilities. application/pdf The one we predicted is called a hemiacetal.) uuid:8834e4cb-f330-4a13-b50f-b3277b62155b This cleavage offers an attractive, alternate stereoselective route to stilbenes in a modified McMurry reaction. /Annots [65 0 R 66 0 R 67 0 R 68 0 R 69 0 R 70 0 R 71 0 R 72 0 R 73 0 R 74 0 R reactivity of aminoboranes is systematically examined. Inter-residual Hydrogen Bonding in Carbohydrates Unraveled by NMR Spectroscopy and Molecular Dynamics Simulations, Synthetic Studies of Kinamycin Antibiotics: Stereoselective Synthesis of the Highly Oxygenated D-Ring and Construction of the ABD-Ring System of Kinamycins, Some observations on the reductive ring opening of 4,6-O-benzylidene acetals of hexopyranosides with the borane trimethylamine–aluminium chloride reagent, A kinetic study on the reductive opening of the diphenylmethylene acetal in methyl 2,3-O-diphenylmethylene-α-L-rhamnopyranoside, Deuterium-isotope study on the reductive ring opening of benzylidene acetals, Quantum chemical studies on the partial hydrogenolysis of methyl 2,3-O-diphenylmethylene-α-L-rhamnopyranoside, Desymmetrization of trehalose via regioselective DIBAL reductive ring opening of benzylidene and substituted benzylidene acetals, Intramolecular Aglycon Delivery Enables the Synthesis of 6-Deoxy-beta-D-manno-heptosides as Fragments of Burkholderia pseudomallei and Burkholderia mallei Capsular Polysaccharide. Cu(OTf)2 is an efficient and dual-purpose catalyst for the highly regioselective reductive ring openings of benzylidene acetals with either BH3 or Me 2EtSiH to give the corresponding primary and secondary alcohols (see scheme). /Subtype /Image endobj However, this does not account for the effect of acids on hydrolytic behavior. /Filter /FlateDecode /Resources << Accordingly, the strong Lewis acidity of boroles in general was nicely demonstrated by the reaction of [Fc(BC(4)Ph(4))] with 4,4'-bipyridine. and A.B. >> The regioselectivity of borane reductions of cyclic acetals can be controlled by the choice of borane. endobj >> thank DST (Unit on Nano Science and Technology) and CSIR, New Delhi, for research fellowships. /MediaBox [0 0 594.95996 840.95996] In hydroboration, BH3-N-phenylamine complexes react rapidly with 1-octene in THF at 25°C, while all other types require refluxing THF or toluene for reaction. << additional organizing element in these complexes. /Resources 97 0 R /Title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o learn about our use of cookies and how you can manage your cookie settings, please see our Cookie Policy. The metal?oxygen bond in some addition compounds of aluminium and gallium trihalides with ethers, NEW SYNTHESES OF β-ALKOXY KETONES AND β-KETO ACETALS, Complexing and exchange of boron, aluminum, and gallium chlorides with some Lewis bases, THE RELATIVE EASE OF REDUCTIVE CLEAVAGE OF 1,3-DIOXOLANES AND 1,3-DIOXANES IN ETHER SOLUTION BY LiAlH4–AlCl3, THE INFLUENCE OF SUBSTITUENTS ON THE EASE AND DIRECTION OF RING OPENING IN THE LiAlH4–AlCl3 REDUCTIVE CLEAVAGE OF SUBSTITUTED 1,3-DIOXOLANES, Chemo-, stereo- and regioselective hydrogenolysis of carbohydrate benzylidene acetals. endobj endobj
/ML 4 << In acetic acid or in the presence of mineral or Lewis acids, a bimolecular attack of the BH3-amine complex on the protonated carbonyl group has been considered to be the most viable mechanistic pathway. 118 0 R 119 0 R 120 0 R 121 0 R 122 0 R 123 0 R 124 0 R] endobj We thank DST and CSIR, India for financial support and DST-FIST for providing NMR facilities. 9. We envisaged that due to steric and electronic consequences, benzylidene acetals should undergo facile and stepwise cleavage with LVT. Catalytic reductive cleavage of methyl α-D-glucoside acetals to ethers using hydrogen as a clean reductant, Synthesis of carbohydrate building blocks via regioselective uniform protection/deprotection strategies, Simultaneous Application of Arylmethylene Acetal and Butane Diacetal Groups for Protection of Hexopyranosides: Synthesis and Chemoselective Ring-Opening Reactions, Greene's Protective Groups in Organic Synthesis: Fifth Edition, Reduction of O,O-, N,O-, and S,O-Acetals to Ethers, Synthesis of the tetrasaccharide glycoside moiety of Solaradixine and rapid NMR-based structure verification using the program CASPER, Regioselective acylation, alkylation, silylation and glycosylation of monosaccharides, Reactions of aldehydes and ketones and their derivatives, A Direct Method for the Efficient Synthesis of Benzylidene Acetal at Room Temperature, ChemInform Abstract: Regioselective Reductive Openings of 4,6-Benzylidene Acetals: Synthetic and Mechanistic Aspects, On the stereoselective opening of chiral dioxane acetals. /Type /Metadata /BitsPerComponent 8 The addition of water to the BH(3) x NMe(3)-AlCl(3)-THF results in faster reactions. Analogous results were obtained for the AlBr3-THF system but for the ionic dissociation. polymerization, its potential as a Lewis acid catalyst for organic transformation is now much more extensive. P.S.K. 2013-10-03T16:29:49+05:30 The mechanisms of regioselective reductive openings of acetals were investigated in several model systems by a combination of Hammett plots, kinetic experiments, density functional calculations, and (11)B NMR. A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution.
The Formyl C—H×××O Hydrogen Bond as a Critical Factor in Enantioselective Lewis-Acid Catalyzed React... Synthesis, Structure, and Reactivity of Borole-Functionalized Ferrocenes. USD 51.00 << In addition, the reduction chemistry of ferrocenylboroles [Fc(BC(4)Ph(4))] and [Fc(BC(4)Ph(4))(2)] has been studied in more detail. Its application in the synthesis of 1,4-dideoxy-1,4-imino-L-xylitol is also highlighted. 6 0 obj 1 0 obj
endobj provides a simple and logical basis for understanding the mechanistic basis /MediaBox [0 0 595.276 841.89] << /BM /Normal This article provides a comprehensive summary of the organic transformations catalyzed by arylboron compounds as acids. /Parent 4 0 R
<< << Effect of structure on the reactivities of representative borane-amine complexes in typical reactions such as hydrolysis, hydroboration, and reduction, Reductive openings of benzylidene acetals.
Nucleophile dependence, Amine Boranes. /Height 320 3099067 In this study 4,6-O-benzylidene acetals were used as model compounds for deciphering the mechanism of regioselective openings using a variety of reducing agents. The reduction of cyclohexanone with BH3-amine complex in THF proceeds by an analogous dissociation mechanism.
/ca 1 In stark contrast the corresponding 4,6-O-benzylidene glucosyl donors are α-selective. 10.1002/(ISSN)1521-3773 /Type /Catalog >> catalyzed by chiral Lewis acids. 24 hours to view or download: of the induced formyl C–H hydrogen bond can serve as a guide in the expansion during the formation of the charge-dipole complex with benzaldehyde. �^#�O1X��|�b[}[��� ����u�+oc[˹�v����)��V^v�����h��sFJyk��t��K�
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JP endobj /ca 1 >> The mechanism of hydrolysis is consistent with the Michaelis−Menten kinetic model. 4 0 obj 12 0 obj /MediaBox [0 0 595.276 841.89]
The latter condition was observed to be compatible with a variety of acid-sensitive functional groups, including allyl and enol ethers. 8 0 obj
/Annots [98 0 R 99 0 R 100 0 R 101 0 R 102 0 R 103 0 R 104 0 R 105 0 R 106 0 R 107 0 R :The benzylidenes are readily formed; in competition between 1,2- and 1,3-diols they will generally form the dioxane. We use cookies to improve your website experience. Regioselectivity and Solvent Dependance, Acyclic stereoselection. ChemInform Abstract: Metal Trifluoromethanesulfonate Catalyzed Regioselective Borane-Reductive Ring Opening of Benzylidene Acetals: A Concise Synthesis of 1,4-Dideoxy-1,4-imino-L-xylitol. The BH(3) x SMe(2)-AlCl(3)-THF system constitutes a borderline case, yielding both free HO-6 (by a first order reaction) and free HO-4 (by a higher order reaction). /BM /Normal /F4 18 0 R
108 0 R 109 0 R 110 0 R 111 0 R 112 0 R 113 0 R 114 0 R 115 0 R 116 0 R 117 0 R �+Sl�V����˗���Gޗ"���%{O���ȇ�,Ej籬s�/�rF �}S��t���6�Z����;[�� for enantioselectivity in many reactions of achiral aldehydes which are 52. Regioselective Oxidative Cleavage of Benzylidene Acetals: Synthesis of [alpha]- and [beta]-Benzoyloxy Carboxylic Acids
The idea Amongst different acetals, benzylidene acetals which have two 0- benzyl bonds are attractive substrates for this study. endobj <<
endobj These reactions include aldol, allylation /Type /Page endobj /F6 20 0 R >> The main advantage of benzylidene acetal is the ability for regioselective openings. This view has been suggested to be applicable to other types of reactions of aminoboranes. m�k���N��
>> The coordination chemistry of ferrocenylboroles was further studied by examining their reactivity towards several pyridine bases.
<<
>> Article Purchase /G3 12 0 R 75 0 R 76 0 R 77 0 R 78 0 R 79 0 R 80 0 R 81 0 R 82 0 R 83 0 R 84 0 R /X13 17 0 R The temperature-dependent reductive cleavage of the 4,6-acetal can be described in terms of kinetic versus thermodynamic control: Lewis-acid coordination of the more accessible O-6 is favored at higher temperatures, whereas protonation of the more basic but sterically encumbered O-4 predominates at low temperatures. effectively restricts rotation about the donor–acceptor bond between >> 3 0 obj /Contents 96 0 R
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