Thiolate syntheses

One example of a copper thiolate synthesis exists in which a disulfide reacts directly with metallic copper without the necessity of an externally applied potential CF3SSCR3 and Cu° cleanly afford the copper(I) perfluoro-alkylthiolate complex [CU 0(SCF3)10(MeCN)8] (58). 

Schemes 110-113 outline the most common general methods for accomplishing the synthesis of thiiranes by formation of a C—S bond (75RCR138,66CRV297, 64HC(19-1)576). The methods in Schemes 111-113 are variations of Scheme 110 they differ in the details of the generation of the thiolate anion which effects the ring closure by a displacement reaction. The methods of converting oxiranes to thiiranes, to be discussed separately (Section 5.06.4.3), involve a displacement like thafof Scheme 110 as the final step.

Tetrazolium-5-thiolate, 2,3-diphenyl-structure, 5, 793 synthesis, 5, 827 Tetrazolium ylides synthesis, 5, 793, 827... 

Treatment of a thiol with a base, such as NaH, gives the corresponding thiolate ion (RS-), which undergoes reaction with a primary or secondary alkyl halide to give a sulfide. The reaction occurs by an Sn2 mechanism, analogous to the Williamson synthesis of ethers (Section 18.2). Thiolate anions are among... 

The conversion of a thiolactone to a cyclic ether can also be used as a key step in the synthesis of functionalized, stereochemically complex oxacycles (see 64—>66, Scheme 13). Nucleophilic addition of the indicated higher order cuprate reagent to the C-S double bond in thiolactone 64 furnishes a tetrahedral thiolate ion which undergoes smooth conversion to didehydrooxepane 65 upon treatment with 1,4-diiodobutane and the non-nucleophilic base 1,2,2,6,6-pentamethylpiperidine (pempidine).27 Regio- and diastereoselective hydroboration of 65 then gives alcohol 66 in 89 % yield after oxidative workup. Versatile vinylstannanes can also be accessed from thiolactones.28 For example, treatment of bis(thiolactone) 67 with... 

Both cis- and (rans-structures are possible RuH2(PMe3)4 is cis (Ru-H 1.507, 1.659 A, Ru-P 2.276-2.306 A) [90] while spectra show that RuH2(PF3)4 and others have this configuration. RuH2[PPh(OEt)2]4 is definitely trans (X-ray) with Ru-H 1.6 A, Ru-P 2.272 A. Many diphosphines form dihydrides. Ru(dmpe)2H2 has been a useful starting material for the synthesis of thiolate complexes [91] such as fra s-Ru(SPh)2(dmpe)2. 

P-Chirogenic phosphine/sulfide hybrid phosphine-boranes 80 were synthesized from the reaction between (l )-tosylates 79 [94] and sodium thiolate in DMF at ambient temperature as depicted in Scheme 12, or alternatively by a one pot synthesis consisting of the nucleophilic attack of the chirally induced hthium salt of 74 on phenyl disulfide. Both methodologies provided the desired sul-fide/phosphine boranes in excellent yields [10]. 

D., Yang, C.-T, Ranford, J.D., Vittal, J.J. and Lee, P.F. (2003) Synthesis, characterization, and biological activities of 2-phenylpyridine gold(lll) complexes with thiolate ligands. Dalton Transactions, (17), 3376. 

Robbins, A.H. and Stout, C.D. (1992) Metallothioneins Synthesis, Structure and Properhes of Metallothioneins, Phytochelatins, and Metal-Thiolate Complexes (eds M.l. ShDman, C.F. Shawlll and KT. Suzuki), VCH Publishers, Weinheim, pp. 31—54. 

---