THE OBSERVATION OF REMARKABLE EFFECTS OF REMOTELY CONNECTED BUT SPATIALLY PROXIMATE HYDROXY-GROUPS ON THE RATES AND REGIOCHEMISTRY OF THE BRICH REDUCTION OF AROMATIC RINGS AND DOUBLE BONDS

DOI: 10.1039/P29840001487

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1487 - 1500 (1984)

Update date:2022-08-04

Topics:

Authors:

Cotsaris, Evangelo

Paddon-Row, Michael N.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/P29840001487

Product and competitive-rate studies of Brich reduction (Li, Bu^tOH, NH3) of a series of alicyclic compounds, (6)-(13), are described.The hydrocarbons (6a)-(8a) and the syn-methoxy derivative (6c) are slowly reduced to give the unconjugated dienes such as (16a).In contrast the syn-alcohols (6b)-(8b) were rapidly reduced to give the monoenes (17), (19), and (22), respectively.Reduction of the syn-alcohol (10b) was also extremely rapid but that of the norbornenols (11a) and (12a) only showed moderate rate enhancements.Each of the above alcohols displays intramolecular OH...? bonding.Brich reductions of (1), (6a), (10a), (11b), and (12b), none of which possess intramolecular OH...? bonds, appear to obey third-order kinetics whereas those of the OH...?-bonded alcohols (6b), (10b), (11a), and (12a) followed a combination of second- and third-order kinetics .The rate and product data for the reduction of the alcohols (6b)-(8b), (10b), (11a), and (12a) are explained in terms of the presence of intramolecular OH...? bonding in these substrates.The observed second-order kinetics are explained in terms of intramolecular protonation of the anion-radical intermediate and is supported by the data for reduction of (6c) and (9).Geometric features which affect the efficacy of intramolecular proton transfer are discussed.Full STO-3G geometry optimisations on the anion radicals of (11a and b) reveal the presence of strong OH...? bonding in the anion-radical of (11a) amounting to some 27 kJ mol^-1.

Full text of DOI:10.1039/P29840001487

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:endo,exo-Tetracyclo<6.2.1.1^3,6.0^2,7>dodecan-11-syn-ol

Cas No:35909-27-4

R&D Labs maybe for 35909-27-4

Nanjing Capatue Chemical Co., Ltd

Contact:+86-25-86371192 +86-025-85720158

Address:No.20 Jiangjun Avenue, Jiangning Economic & Technical Development Zone
BioBioPha Co., Ltd

Contact:+86-871-65217109

Address:132 Lanhei Road, Kunming Institute of Botany, Chinese Academy of Sciences
Nantong LiKai Chemical Co.,Ltd

Contact:+86-513-89068669

Address:Jincheng Science Park
Shenzhen Sungening Medicine Co., Ltd

Contact:+86-871-65110906

Address:Room702, Building 2, 365 Dianchi Road, Kunming, Yunnan Province, P.R. China
Wuhan Chemchemical Co., Ltd.(expird)

Contact:15973022782

Address:7-5-6218,Incubation Centre,Guandong Industry Park, East Lake High-Tech Development Zone,Wuhan City.

Relevant to this article

Bis-, tris-, and tetrakis(squaraines) linked by stilbenoid scaffolds

Doi:10.1002/1099-0690(200107)2001:14<2757::aid-ejoc2757>3.0.co;2-2
(2001)
Selective Metalation of 1,3-Dithiole-2-thiones: An Effective Preparation of New Symmetrically and Nonsymmetrically Tetraarylated Tetrathiafulvalenes

Doi:10.1055/s-0035-1560728
(2016)
Hypervalent λ(n)-iodane-mediated fragmentation of tertiary cyclopropanol systems II: Application to asymmetric syntheses of piperidine and indolizidine alkaloids

Doi:10.1016/S0040-4020(99)00073-3
(1999)
Studies on mitomycins. V. Synthesis of indolequinone and their activities.

Doi:10.7164/antibiotics.24.435
(1971)
Dual Role of Acetate in Copper(II) Acetate Catalyzed Dehydrogenation of Chelating Aromatic Secondary Amines: A Kinetic Case Study of Copper-Catalyzed Oxidation Reactions

Doi:10.1002/ejic.201600540
(2016)
Zeolite nanofiber assemblies as acid catalysts with high activity for the acetalization of carbonyl compounds with alcohols

Doi:10.1039/c3ra47952h
(2014)

Article Doi