Alkenes dimethoxy

Figure 2.9. NMR spectra of 3,4-dimethoxy-p-methyl-p-nitrostyrene (9) [CDCI3, 25 C, 20 MHz], (a, b) H broadband decoupled, (a) complete spectrum with CH3 quartets at Sc = 14.1 and 56.0 (b, c) decoupled and coupled partial spectrum of benzenoid and alkene carbon atoms, (c) obtained by gated decoupling...

Raney Nickel W2 or W4, EtOH, 85-100% yield. Mono- and dimethoxy-substituted benzyl ethers and benzaldehyde acetals are not cleaved under these conditions, and trisubstituted alkenes are not reduced. 

Several investigators have studied intramolecular Heck reactions on alkene-tethered haloindoles. Black prepared several l-allyl-7-bromoindoles and found that they undergo cyclization in the presence of palladium as shown for 242 to 243 [267]. Although this new synthesis of pyrroloquinolines is reasonably general, some of the products are unstable. Substrate 242 was prepared by bromination of 4,6-dimethoxy-2,3-diphenylindole (92%) and //-alkylation. 

Disubstituted alkynes and terminal alkynes form E-dibromoalkenes [4] when the tribromide is formed in situ in an essentially basic medium, an addition reaction followed by elimination of hydrogen bromide results in the conversion of terminal alkynes into the 1-bromoalkynes [5]. When the addition reaction is conducted in methanol, l,l-dibromo-2,2-dimethoxyalkanes are produced, in addition to the 1,2-dibromoalkenes [6], The dimethoxy compounds probably result from the initial intermediate formation of bromomethoxyalkenes. Under similar conditions, alkenes yield methoxy bromo compounds [7]. 

Anodic addition converts enolacetates into a-acetoxyketones or enones, depending on the reaction conditions [135], conjugated dienes into 1,2- or 1,4-dimethoxy alkenes [65], and hydroquinone dimethyl ethers into quinone bisketals [136, 137]. Anodic addition also affords products, some of which are of industrial interest, such as propylene oxide [138a] or 1,4-dimethoxydihydrofuran [138b]. To... 

Electrochemical oxidation of 2,6-dimethoxy-4-allylphenol in aqueous methanol buffered with sodium hydrogen carbonate gives similar amounts of 2- and 4-methoxy substitution products, fhe 2-methoxylated product readily undergoes a Diels-Alder reaction with itself. The dimer 19, the natural product asatone, is found in some 1 % yield and most of the 2-methoxylated product is lost by addition of the ally alkene bond across the diene system of a second molecule [109]. 

Only two examples of the synthesis pyrimidoazocines have been described. In Ref. 82JHC1257, a three-stage synthesis of a new heterocycle system, pyrimido[5,4-c]benz[l]azocine, has been proposed. Condensation of 4-methyl-2-phenyl-5-pyrimidincarboxylate (112) with 3,4-dimethoxy-6-nitrobenzaldehyde (113) led to the substituted alkene 114, which, after catalytic hydrogenation of the nitro group on Raney nickel and subsequent intramolecular cyclization of product 115, was converted into pyrimidobenz[l]azocine 116 (Scheme 32). 

Mit vielfach guten Ausbeuten verlauft die folgende, zweistufige Alternative zur Mannich-Reaktion, bei der ein Alkyl-keton zunachst durch Umsetzung mit Dimethoxy-dimethyl-amino-methan (oder auch mit Bis-[dimethylamino]-tert.-butyloxy-methan) in ein 1-Ami-no-3-oxo-l-alken iibergefuhrt wird, das isoliert und mit Lithium-alanat zum Mannich-Produkt reduziert wird2. 

There are several examples of arylnitrenium ion additions to alkenes (Fig. 13.54). For example, Dalidowicz and Swenton trapped A-acetyl-A-(4-methoxyphenyl)-nitrenium ion 112 with 3,4-dimethoxy-l-propenylbenzene and isolated products resulting from addition of the alkene to the ortho position of the nitrenium ion, giving cation 113, followed by its cychzation onto N (yielding 114) or the acetyl carbonyl group (yielding 115). 

The combination of rhodium dicarbonyl acetylacetonate complex (Rh(acac)(CO)2) and a diphosphite ligand, (2,2 -bis[(biphenyl-2,2 -dioxy)phosphinoxy]-3,3 -di-/i t/-butyl-5,5 -dimethoxy-l,T-biphenyl (BIPHEPHOS), is an excellent catalyst system for the linear-selective hydroformylation of a wide range of alkenes. This catalyst system has been successfully applied to the cyclohydrocarbonylation reactions of alkenamides and alkenylamines, which are employed as key steps for the syntheses of piperidine,indolizidine, and pyrrolizidine alkaloids. ... 

The oxidation of terminal alkenes with an EWG in alcohols or ethylene glycol affords acetals of aldehydes chemoselectively. Acrylonitrile is converted into l,3-dioxolan-2-ylacetonitrile (69) in ethylene glycol and to 3,3-dimethoxy-propionitrile (70) in methanol[28], 3,3-Dimethoxypropionitrile (70) is produced commercially in MeOH from acrylonitrile by use of methyl nitrite (71) as a unique reoxidant of Pd(0). Methyl nitrite (71) is regenerated by the oxidation of NO with oxygen in MeOH. Methyl nitrite is a gas, which can be separated easily from water formed in the oxidation[3]. 

The condensation of a,/3-unsaturated carbonyl compounds with phenols has received much attention as a route to chromenes. Problems associated with the instability of alkenals have been largely overcome by the use of masked forms of these reagents. The derived acetals have proved particularly useful in this respect. It is also advantageous to use the acetals of hydroxyalkanals and to introduce the double bond during the course of the reaction. Thus, 4,4-dimethoxy-2-methylbutan-2-ol serves as the equivalent of the unstable 3-methylbut-2-enal. 

CH2 =CHCH2CsCR, add only two molecules of methanol under the same conditions to yield 5,5-dimethoxy-l-alkenes, CH2 =CHCH2CH2C(OCHj)2R. Reaction of 1-chloro- or 1-bromo-heptyne, C, H,C = CX, in the same way gives the corresponding 1-halo-2,2-dimethoxyheptanes, CjH C(OCHj)2CH2X, in 30 and 60% yield, respectively. ... 

From Methyl 2,4-Dimethoxy-6-methyipyrimidine-5-carboxylates and Acetylenes or Alkenes... 

A cyclic iminocarbene was transferred from 2-diazo-5-isopropyl-3,6-dimethoxy-2,5-dihy-dropyrazine to an alkene under unusually mild conditions. This diazo compound decomposes under the conditions of its synthesis from 2,5-dihydropyrazine 8, and in the presence of cy-cloalkenes, 2,5-dihydrospiro[pyrazine]bicyclo[n.l.O]alkanes 9 (n = 3-5) were obtained (an experimental procedure is given in Houben-Weyl Vol. E19b, pi 194). 

After the solution of 3,3-dimethoxy-3//-diazirine thus obtained was mixed with the alkene, the corresponding 1,1-dimethoxycyclopropanes were formed in good yield. ... 

Thermal decomposition of 7,7-dialkoxynorbornadiene derivatives in the presence of an alkene requires rather high temperatures ( 125°C) l,2,3,4-tetrachloro-7,7-dimethoxy-5-phenylbicyclo[2.2.1 ]hepta-2,5-diene is the most often applied source of dimethoxycarbene. Electrophilic alkenes such as )- and (Z)-but-2-enedioates and cinnamates, styrene derivatives, " 1-phenylbuta-l,3-diene etc. undergo addition of this carbene across the double bond to give 1,1-dimethoxycyclopropanes 2. 

Gallc er and co-workers devised a formal enantioselective synthesis of ( — )-3 in wduch the stereogenic center at C-6 was derived fiom Cbz-protected (S)-2-amino-4-pentenoic acid (36) (44). Acylation of 3,3-dimethoxy-pyrrolidine (37) with this acid yielded amide 38, which was converted into aldehyde 39 by cleavage of the terminal alkene vnth osmium tetroxide and sodium periodate (Scheme 5). The indolizidine nucleus was constructed from 39 by a problematic intramolecular aldol condensation, which was eventually optimized by using 2,2,6,6-tetramethylpiperidine as base followed by adsorption onto, and elution from, silica gel (45). Diastereoselective reduction of the ketone group of the aldol product 40 was accomplished in better than 95% enantiomeric excess (ee) with the Corey... 

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