Cherkasov R.

Kutyrev G.

Pudovik A.

Tetrahedron

Kazan Federal University Digital Repository

Tenahdron Vol. 41, No. 13. pi. 2567 to 2624.1985 oo4Mo2olss smo+ .oo Printed In Great Britalo. PergrImm Press Lid. TETRAHEDRON REPORT NUMBER 186 ORGANOTHIOPHOSPHORUS REAGENTS IN ORGANIC SYNTHESIS R. A. CHERKASOV, G. A. KUI-YREV and A. N. P~JDOVIK* Kazan State University, Kazan, U.S.S.R. (Received in UK 9 May 1984) CONTENTS 1. Phosphorus Thioacids and their Derivatives . . . . _ . . . . . . . . . . . . 2568 1.1. O,S-Interchange reactions . . . . . . . . . . . . . . . . . . . . . . . 2568 1.2. Reactions with compoundscontainingmultiple carbon-nitrogen bonds . . . . . . 2572 1.3. Other synthetic uses of phosphorus thioacid derivatives . . . . . . . . . . . . . 2578 2. Combined Reagent-Triphenylphosphine-thiocyanogen . . . . . . . . . . . . . 2582 3. Lawesson’s Reaeent (LR) . . . . . . . . . . . . . . . . . . . . . . 2588 3.1. 3.2. 3.3. 3.4. Reactions &h &b&y1 compounds ................... 3.1.1. Ketones ........................... 3.1.2. Esters of carboxylic and thiocarboxylic acids .............. 3.1.3. Amides of carboxylic acids. .................... 3.1.4. Hydrazides of carboxylic acids ................... Synthesis of sulfur-containing heterocyclic compounds ............. Synthesis of phosphorus- and sulfur-containing heterocycles ........... Reactions with compounds containing element-oxygen bonds. .......... 2589 2589 2592 2594 2598 2601 2608 2618 Organophosphorus compounds are widely used in organic synthesis.’ The use of phosphorus ylides- Wittig reagents-for the synthesis of unsaturated systems is well known.‘*’ Various derivatives of pentacoordinated phosphorus have served as valuable initial substances in the molecular design of bioorganic structures. 3*4 One can hardly overestimate he importance of phosphine,’ phosphoryl,‘j and phosphacyclane7 metal complexes in the development of the chemistry of organometallic ompounds and metal-complex catalysis. Great progress has been made in the application of combined reagents- tertiary phosphine, di- or polyfunctional organic compounds-for the functionalization of organic substrates.*sg Inorganic phosphorus compounds have found an extensive application in synthetic organic chemistry for the purposes of halogenation, thionation and in other preparative problems.rO*’ ’ The most frequently used thionating agent, mainly for carbonyl-containing substrates, is phosphorus pentasulfide, P4S,0.‘2 In recent years a new area of intensive development has appeared in the application of organophosphorus compounds in organic synthesis. This involves the use of organothiophosphorus reagents which not only introduce a sulfur atom into organic substances but also permit other synthetic operations. As a rule, such processes are characterized by a high regio- and, sometimes, also stereoselectivity, and almost in all cases by exceptional efficiency : the yields of required products are usually from satisfactory to quantitative. In the present review an attempt has for the first time been made at summarizing and systematizing the methods of using in organic synthesis the new thionating and functionalizing reagents: (i) derivatives of phosphorus thio- and dithioacids, (ii) triphenylphosphine-thiocyanogen (TPPT) combined reagent and (iii) p-methoxyphenylthiophosphine sulfide dimer (Lawesson’s reagent-LR). The driving force of many of these reactions involving organothiophosphorus reagents is the formation of stronger P=O and P-O bonds instead of labile P=S and P-S bonds.r3 An important contribution to the reaction energetics is made by the transformation of intermediate Cmembered heterocycles or intermediate phosphorane structures into more stable 6-membered cyclic or acyclic 2567 

Tetrahedron report number 186. Organothiophosphorus reagents in organic synthesis

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Tetrahedron report number 186. Organothiophosphorus reagents in organic synthesis

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