2-Lithio-l,3,5-trithiane

Octamethylenediamine, 54, 88 n-Octanal, from 2-lithio-l,3,5-trithiane and 1-bromohep-tane, 51, 43 1—Octanol, 53, 79 trans-2-Octnal, 54, 27... 

ITS DIMER, 52, 77 Methyl D-Norandrost-5-en-3 g-ol-166-carboxylate, 52, 56 (S)- (-) - 3-Methylpentanal, from 2-lithio-l,3,5-trithiane and (S)-(+)-l-iodo-2-methy 1-butane, 51, 43... 

Lithio-l,3-dithiane and 2-lithio-l,3,5-trithiane have been transformed into 2-substituted benzylamines 273 and 274, respectively, by reaction with a mixture of benzaldehyde and lithium hexamethyl disilazide449. In the case of compound 266, the corresponding derivatives 275 and 276 have also been prepared. Related compounds were used for the preparation of photolabile molecular hosts. 

An alternate route not involving 2-lithio-l,3,5-trithianes for the preparation of 2-substituted-l,3,5-trithianes recently has been reported . This method involves reaction of an aldehyde 77 with the dithiol 78 to yield the 2-substituted trithiane 79. 

S)-(-)-3-Methylpentanal, from 2-lithio-1,3,5-trithiane and (SH+)-l-iodo-2-methylbutane, 51,43... 

The methylations of l,3-dilithio-5,7-dimethyl-2,4,6,8-adamantane and of 1,3,5,7-tetrathiacyclooc-tane tetraanion- are of theoretical value only. 1,3,5-Trithiane and both mono- and 2,4,6-trialkyl-substituted derivatives have been metallated - with n-butyllithium and alkylated - with reactive alkylating agents such as primary alkyl iodides or bromides and benzyl bromide (Scheme 73, entries a and b). The metallation of monoalkylated trithianes occurs at one of the two unsubstituted sites and leads eventually to the product having both substituents in the equatorial position. - Thus the high equatorial preference for lithium in 2-lithio-l,3-dithiane is also present in 2-lithio-2-methyl-l,3,5-trithiane. Mer-... 

Trithianes (74) undergo lithiation with an equivalent of /i-butyllithium to yield the 2-Iithio derivatives, which substances undergo the usual reactions (equation 67) as with 2-lithio-l,3-dithianes. Since additional active hydrogens are present in 1,3,5-trithianes, dimethyladon has been observed in some cases. ... 

Lactones, addition of thiols 769 Lead, thiol derivatives 748, 749 Lipoic acid 637-639 Lithiation, of 1,3-dithiane 536 of 1,3,5-trithiane 546, 547 2-Lithio-l,3-dithianes, for preparation of 1-deuterioaldehydes 547 for preparation of orthothioformate 547... 

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