Tosylate groups

The hydrogenolyaia of cyclopropane rings (C—C bond cleavage) has been described on p, 105. In syntheses of complex molecules reductive cleavage of alcohols, epoxides, and enol ethers of 5-keto esters are the most important examples, and some selectivity rules will be given. Primary alcohols are converted into tosylates much faster than secondary alcohols. The tosylate group is substituted by hydrogen upon treatment with LiAlH (W. Zorbach, 1961). Epoxides are also easily opened by LiAlH. The hydride ion attacks the less hindered carbon atom of the epoxide (H.B. Henhest, 1956). The reduction of sterically hindered enol ethers of 9-keto esters with lithium in ammonia leads to the a,/S-unsaturated ester and subsequently to the saturated ester in reasonable yields (R.M. Coates, 1970). Tributyltin hydride reduces halides to hydrocarbons stereoselectively in a free-radical chain reaction (L.W. Menapace, 1964) and reacts only slowly with C 0 and C—C double bonds (W.T. Brady, 1970 H.G. Kuivila, 1968). 

Dialkylation of an amine or sulfonamide with a 1,3-dihalide provides a further route to azetidines <79CRV33l, 64HC( 19-2)88 5). Examples of this approach are the formation of N-tosylazetidine from tosylamide and l-bromo-3-chloropropane and the formation of N-alkylazetidinyl esters (36). The latter reaction works well except for R=Me the former provides a useful route to azetidine since the tosyl group can be removed by reductive methods. 

The THP ether can be converted directly to an acetate by refluxing in AcOH/AcCl (91 % yield). These conditions would probably convert other related acetals to acetates as well. The THP group can also be converted through the 0-SnBu3 to benzyl, MEM, benzoate, and tosylate groups. ... 

The tosyl group has also been removed by reductive cleavage with Na/NH3 (65-73% yield), Na/naphthalene (50-87% yield),and Na(Hg)/MeOH (96.7% yield)."... 

Sodium naphthalenide. This reagent has been used to remove the tosyl group from an amide. ... 

It is interesting to note that although the first examples of template effects were observed in nitrogen macrocycles (see chapter 2) no template effect appears to operate in the synthesis of 72. Richman and Atkins note this in their original report . The authors replaced the sodium cation with tetramethylammonium cations and still obtained greater than 50% yield of tetra-N-tosyl-72. Shaw considered this problem and suggested that because of the bulky N-tosyl groups, .. . the loss of internal entropy on cyclization is small He offered this as an explanation for the apparent lack of a template effect in the cyclization. 

Migration of a BOC is normally not observed, but in the following case a BOC group moved to a hydroxyl. The stabilizing effect of the tosyl group makes this possible. ... 

In general, the benzenesulfonyl group is somewhat more reactive than the tosyl group, in both its formation and ease of cleavage. 

In 1972, van Leusen, Hoogenboom and Siderius introduced the utility of TosMIC for the synthesis of azoles (pyrroles, oxazoles, imidazoles, thiazoles, etc.) by delivering a C-N-C fragment to polarized double bonds. In addition to the synthesis of 5-phenyloxazole, they also described reaction of TosMIC with /7-nitro- and /7-chloro-benzaldehyde (3) to provide analogous oxazoles 4 in 91% and 57% yield, respectively. Reaction of TosMIC with acid chlorides, anhydrides, or esters leads to oxazoles in which the tosyl group is retained. For example, reaction of acetic anhydride and TosMIC furnish oxazole 5 in 73% yield. ... 

Although this particular series of reactions involves nucleophilic substitution of an alkyl p-toluenesulfonate (called a tosylate) rather than an alkyl halide, exactly the same type of reaction is involved as that studied by Walden. For all practical purposes, the entire tosylate group acts as if it were simply a halogen substituent. In fact, when you see a tosylate substituent in a molecule, do a mental substitution and tell yourself that you re dealing with an alkyl halide. 

Replacement of the tosylate group in 35 with a saturated butyl chain is achieved with an excess of lithium di-n-butylcuprate and, after hydrolytic cleavage of the isopropylidene and ethoxyethyl (EE) protecting groups, lactone 23 is obtained in an overall yield of... 

A highly efficient construction of the steroidal skeleton 166 is reported by Kametani and coworkers111 in the intramolecular Diels-Alder reaction of the a, jS-unsaturated sulfone moiety of 165 (equation 117). Thus, when the sulfone 165 is heated in 1,2-dichlorobenzene for 6h, the steroidal compound 166 can be obtained in 62% yield. The compound 166 produces estrone (167) by elimination of benzenesulfinic acid and subsequent hydrogenation of the formed double bond. The stereoselectivity of the addition reflects a transition state in which the p-tosyl group occupies the exo position to minimize the steric repulsion between methyl and t-butoxy groups and the o-quinodimethane group as shown in equation 117. 

Alkyl halides and tosylates react with Na2pe(CO)4 in the presence of ethylene to give alkyl ethyl ketones. The reaction was not successful for higher alkenes, except that where the double bond and the tosylate group are in the same molecule, five- and six-membered rings can be closed. ... 

An electrochemical method for amination has been reported by Shono et al. Derivatives of malonic esters containing an N-tosyl group were cyclized in high... 

The optimum results were obtained with Grignard reagents in the presence of 10 mol % of Cu(I)CN. The stereochemical course of this MIRC reaction can be explained by adopting Yamamoto s model for conjugate addition of cyano-cuprates to y-alkoxy-a,)5-unsaturated esters (Fig. 2) [35]. In this model, it is proposed that the larger substituent (L), in our case the tosyl group, will adopt the... 

The presence of transition metal ions has a catalytic effect on reduction of halides and tosylates by LiAlH4.166 Various copper hydride reducing agents are effective for removal of halide and tosylate groups.167 The primary synthetic value of these reductions is for the removal of a hydroxy function after conversion to a halide or tosylate. 

Tri-O-acetyl-a-D-xylopyranosyl bromide106 (138) and N-tosyl-L-serine methyl ester107 (139) were condensed in the presence of Drierite and silver oxide, and then the O-acetyl and methyl ester groups were removed by treatment with sodium hydroxide, and the N-tosyl group by means of sodium in liquid ammonia, to give 140. Synthesis of this compound has also been described by other workers108-110 and the a-D an-omer by Brendel and Davidson.108... 

In order to synthesize quinolizidine compounds, some authors have used the Parsons method (Bu3SnH/AIBN) to cleave the iV-tosyl group of 2-piperidones such as 144 (AIBN = 2,2 -azobisisobutyronitrile). After detosylation to 145, the intramolecular cyclization of the lactam promoted by sodium hydride gave quinolizidinone 146. T reatment of this compound with Raney nickel both cleaved the C-S bond and reduced the C=C bond to give quinazolinone 147, while the lactam carbonyl was reduced with LiAlH4 to give 148 (Scheme 23) <2005TL8551>. 

The perhydropyrazino[l,2- ]pyrazine 247 was obtained in good yield when the tosyl groups of the macrocycle 246 (prepared from N-tosylated diethylenetriamine and l,3-dichloro-2-propanol) were removed (Equation 28)... 

The same reaction with acetaldehyde produces carbene complex 34 with a saturated ring, i.e., an oxazolidin-2-ylidene ligand with the tosyl group replaced by methoxide. 

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