Lithium precursors

Alternatively, alkoxycarbene complexes are formed upon alcoholysis of strongly electrophilic acyloxycarbene complexes 16 [26] generated by in situ acylation of tetraalkylammo-nium acyl metalates 15. These compounds are obtained from lithium precursors 11 and can be stored in a refrigerator for months. This is the method of choice for the synthesis of chiral metal carbenes 17 bearing terpene or sugar auxiliaries (Scheme 9). 

DETERMINATION OF TRITIUM RADIONUCLIDE AND LITHIUM PRECURSOR IN MAGNOX REACTOR STEELS... 

Determination of Tritium Radionuclide and Lithium Precursor in Magnox Reactor Steels 139... 

Numerous complexes with general formula (78) have been reported which are prepared by the reaction of the metal halides C0CI2 or NiBr2 and (CH2) [R2P=NAr2]2 (R = Me, Ph) in absence of a lithium precursor. Complexa-... 

Wang, D. et al. New solid-state synthesis routine and mechanism for LiFeP04 using LiF as lithium precursor. J. Solid State Chein., 177,4582 (2004]. 

Several substituted cyclohexane derivatives may also be obtained by the reduction of a benzenoid precursor. Partial reduction of resorcinol, for example, and subsequent methyla-tion yields 2-methylcyclohexane-I,3-dione, which is frequently used in steroid synthesis (M.S. Newman, 1960 see also p. 71f.), From lithium-ammonia reduction of alkoxybenzenes l-alkoxy-l,4-cyclohexadienes are obtained (E.J. Corey, 1968 D). 

Interest in the synthesis of 19-norsteroids as orally active progestins prompted efforts to remove the C19 angular methyl substituent of readily available steroid precursors. Industrial applications include the direct conversion of androsta-l,4-diene-3,17-dione [897-06-3] (92) to estrone [53-16-7] (26) by thermolysis in mineral oil at about 500°C (136), and reductive elimination of the angular methyl group of the 17-ketal of the dione [2398-63-2] (93) with lithium biphenyl radical anion to form the 17-ketal of estrone [900-83-4] (94) (137). 

K.S. Tunison and Y.M. Gupta, Effects of Surface Preparation on Elastic Precursor Decay in Shocked Pure Lithium Fluoride, Appl. Phys. Lett. 48, 1351-1353 (1986). 

S.E. Arione and G.E. Duvall, Temperature Dependence of the Precursor Amplitude in <111 > Lithium Fluoride, in Shock Waves in Condensed Matter (edited by Y.M. Gupta), Plenum, New York, 1986, pp. 299-302. 

Lithium insertion in microporous hard carbons (region 3 in Fig. 2) is described in section 6. High capacity hard carbons can be made from many precursors, such as coal, wood, sugar, and different types of resins. Hard carbons made from resole and novolac resins at temperatures near 1000°C have a reversible capacity of about 550 mAh/g, show little hyteresis and have a large low voltage plateau on both discharge and charge. The analysis of powder X-ray diffraction. 

Some advantages of this reaction are high yield if the tosylate is in a sterically accessible position excellent isotopic purity of the product (usually higher than-95%) and perhaps most important, access to stereospecifically labeled methylene derivatives. For example, deuteride displacement of 3j -tosylates (183) yields the corresponding Sa-d derivative (185) in 96-98% isotopic purity. Application of this method to the labeled sulfonate (184), obtained. by lithium aluminum deuteride reduction of a 3-ketone precursor (see section HI-A) followed by tosylation, provides an excellent synthesis of 3,3-d2 labeled steroids (186) without isotopic scrambling at the adjacent positions. The only other method which provides products of comparable isotopic purity at this position is the reduction of the tosyl-hydrazone derivative of 3-keto steroids (section IV-B). 

Thus the critical synthetic 1,6-dihydropyridine precursor for the unique isoquinuclidine system of the iboga alkaloids, was generated by reduction of a pyridinium salt with sodium borohydride in base (137-140). Lithium aluminum hydride reduction of phenylisoquinolinium and indole-3-ethylisoquinolinium salts gave enamines, which could be cyclized to the skeletons found in norcoralydine (141) and the yohimbane-type alkaloids (142,143). 

Isothiazole forms the carbenes upon treatment of its lithium salt with [CfiF5Au(THT)] and methyl triflate while the C-coordinated complex formed before methylation was not isolated. When [Ph3PAuCl] is used as the precursor, both C-coordinated complex and then carbene can be prepared (95JCS(D)2067). 

A substituted benzoic acid serves as precursor for the nontricyclic antidepressant bipena-mol (175). Selective. saponification of ester 171 afford.s the half-acid 172. Reaction of the acid chloride derived from this intermediate (173) with ammonia gives the amide 174. Reduction of the last by means of lithium aluminum hydride gives bipenamol (175) [44]. 

The Michael additkin of Lithium etiolates to tiitroalkenes folbwed by reaction with acetic anhydnde gives acetic niironic anhydndes, which are good precursors for 1,4-diketones, pyrroles, and pyrrolidines fEq. 10.73. ... 

The product i n this case is a cis-disubstituted alkene, so the fi rst question is, " What is an immediate precursor of a cis-disubstituted alkene " We know that an alkene can be prepared from an alkyne by reduction and that the right choice of experimental conditions will allow us to prepare either a trans-disubstituted alkene (using lithium in liquid ammonia) ora cis-disubstituted alkene (using catalytic hydrogenation over the Lindlar catalyst). Thus, reduction of 2-hexyne by catalytic hydrogenation using the Lindlar catalyst should yield cis-2-hexene. 

Removal of the carbonate ring from 7 (Scheme 1) and further functional group manipulations lead to allylic alcohol 8 which can be dissected, as shown, via a retro-Shapiro reaction to give vinyl-lithium 9 and aldehyde 10 as precursors. Vinyllithium 9 can be derived from sulfonyl hydrazone 11, which in turn can be traced back to unsaturated compounds 13 and 14 via a retro-Diels-Alder reaction. In keeping with the Diels-Alder theme, the cyclohexene aldehyde 10 can be traced to compounds 16 and 17 via sequential retrosynthetic manipulations which defined compounds 12 and 15 as possible key intermediates. In both Diels-Alder reactions, the regiochemical outcome is important, and special considerations had to be taken into account for the desired outcome to. prevail. These and other regio- and stereochemical issues will be discussed in more detail in the following section. 

The formation of 2-(t-butyl)-2-trimethylsilyl-2//-thiopyran has recently been reported from 1-substituted 1,3-butadienes with /-BuCSSiMe3 (92MI1) (see Scheme 2). An unusual product with proposed structure 47b has been reported (84JOC5143) from benzothiopyrone 46 on reaction with sec-butyl lithium (46 - 47a — 47b, Scheme 3) on the basis of spectroscopic data. 6-Methylthio-2//-thiopyran was isolated after the flash vacuum thermolysis of more complex starting precursors (93TL2605). 

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