10urnal of Scientific & Industrial Research Vo1.59, April 2000, pp 265-279
Methods of Synthesis and Properties of 1-Vinylsilatranes* + M Nasim and PS Venkataramani Defence Materials & Stores Research & Development Establi shme nt, DMSRDE PO, GT Road, Kanpur 208 01 3 and G S Zaitseva Chemistry Department, M oscow State University, B-234, Vorob Evy Gory, 119899, M oscow, Russ ia
The sy nthesis and chemical reactivity of I-vinylsilatranes have been reviewed. Chemical reactions of I-vi nylsil atranes such as cycloaddition, oxidation, hydrosi lylati on and derivatisation have been discussed in detail. Literature available/publi shed till the end of 1998 have been covered.
1 Introduction itself, the simplest compound of thi s class has structure II, where R= H, M =Si. The chemistry of organo compounds of IYB group elements (Si, Ge, and Sn) is one of the fascinating areas having practical utility l-4. Compared to th e organocompounds of silicon and tin , the l)2 ~~__ C!h organogermanium compounds are comparatively less H/Hi 1 H, studied and are not widely used in practice. This is be \4-A1- o I cause of relatively hi gh cost of the starting germanium R source such as germanium metal and its oxide. How ever, during recent years, spec ific and prospective prac (I) (11) ti cal applications of organogermanium compounds have been established in terms of its bi ological and pharma Figure I - (I) Depicts heterocyclic skeleton (M=metal) and (II ) cological activity3- JO. depicts si latrane (R= H, M=Si) Now-a-days intensive and useful research is being Metall atranes having cage structure are a class of carried out in the field of organo derivatives of sili con, pentacoordinated organometallic compounds formed germanium, and tin in which the metal atom present has from th e reacti on of trialkanolamines such as tri eth the coordination number differing from four. In the se anolamine with trifunctional si lanes, germanes or ri es of pentacoordinated compounds, a special pl ace is stannanes, [RM(OR)3]' These are characterized by occupied by the cyclic compounds of silicon, germanium transannular donation of electron density from nitrogen and tin derivatives of triethanolamine and its homol ogue to th e metal atom, thereby producing an effective 2Y 3 pentacoordination at sili con or germanium -32 called sil atranes2.11 -21, germatranes .4.22 and stannatranes 23- 26, respectively. In general, th ese compounds are classi Syntheses of new sil atranes are of mu ch interest in fied under "metallatranes" as proposed by Yoronkov et view of their interesting biologicaI2.:n-3\ physicochemi ai. 27.2X. The chemical nomenclature is l-organyl-2,8,9- caP6-39 , and structural properti es 40-47 . Chemical investi trioxa-5-aza- l-metalla (s ila, germa, or stanna) tricyclo gati ons of these hypervalent sili con species are being 4x 50 [3.3.3.0 15] undecanes. intensively pursued - . Their heterocyclic skeleton is depicted in struc Silatranes are technologically important materials ture-I, where M stands for metal (Figure I). Silatrane in view of their potential applications in rodenti cides 'il , 34 in secti cides , crop yield enhancement3'i.'i2 , medicine (wound healing, intensification of hair growth-treatment *DMSRDE Reference No. 2528. of diffe rent kind of alopecia)2.35, agrochemicals + Author for correspondence. 266 J SCI INO RES VOL.59 APRIL 2000
(microbic ides, bactericides, fungicides and an ti cancer It became poss ib le for S amo ur ~() to synthes ize 1- agents)53-S\ polymers and compos ite materi als (curing vin yl-(3,7, I O-trimethyl)s il atrane (6) by the above meth od agents for a number of synthetic res in s, key in g coupling using triisopropanolamine (5). agents?.5fi.S7 , textiles (water and oil repellents)\ corro sion inhibitor2.5x.59 , seri culture (s ilk produ ction)35.oo, conservating agent (fish conservati onf. Silatranes are 2 of certain practi cal interest as suitable alkylatin g , 3 5 alkenylating2, arylating2 and reducin g agentsh l for th e CH =CHSi [OCH(CH )CH N + 3EtOH preparati on of very pure organi c deri vati ves of heavy 2 3 2J3 2 metals . 6 The practical application of sil at ranes are not lim However, in this method the reactants were sub ited. The combinati on of the sil atrane moiety with jected to prolon g heatin g for completi on of the reacti on. organometallics should be of interest whi ch can be used Addition of catalytic amounts of sodium or potassi um as redox potenti aP9 and also of technological importance alkox ide in the reacti on mi xture shortened th e reaction e.g. non linear opti c materi als21. Group 13 azatranes time. Thus, Voronkov et af. X2 sy nthesised compound 1 (azaalumatranes, azagall atranes) and group 14 azatranes and its C-methyl su bstituted (in the afrane cycle) ana (azas il atranes, azagermatranes etc) wi ll be futuristic po logue by th e transesterificati on of compound 2 wit h tential MOCVD agents fo r metal and non-met I nitrides tri s(2-alk anolamines) in th e pr sence of 10 per cent film precursorso2.o3 . meth anoli c so luti on of sodium meth oxi.de. Recently, we initiated in ves ti gating the sy nthesis + and chemical properties of functionali sed sil atranes4s -47.o4-69, and (McO),Si CH=CH, N(C H, CH,O H)"(CH,CHOH),.,, 7X 2 CH, I germatranes70- . A large number of fun cti onali zed 211 13 -- N(CH,CH,O)" (C H,CHO),."SiCH=CH, + 3MeOH sil atranes havin g become avail abl e in earlier years . . • CH, I Our main attrac ti on was fo r l-vin ylsil atranes sin ce 7,8 in our hands th ese proved to be excell ent precurso r ma n = I (87 per celli) (7); n = 2 (85 per celli) (8) teri als for the synthesis of several new fun c; ti onli sed sil atranes. Thus the paper su mmari zes the numerou s data Intermolecul ar condensati on of si Iylether deri va avail able on I-vinylsil atranes, hi ghli ghti ng, both their tives of di oxaazasil ocanes (9-11) containing a phenyl preparati ve aspects as we ll as reacti vity. The literature group at sili con gave compound 1. Reaction proceeded up to the end of 1998 is covered here. onl y in the presence of sodium alkox ide to yield com pound 1 in 70-80 per cent yieJdK3. 2 Methods of Synthesis of 1-Vinylsilatranes
I-Vinylsilatrane, N(CH CHP\SiCH=CH (1), was "ACH,CH2 . 2 2 , fir t prepared by Frye et af. 79 by transesterifi cation of RRIS( >-CH2CH20R2 + (AlKOhSiCH=CH --> OCH2CH2 vinyltri al koxysil anes (2, 3) with tri eth anolami ne (4). 9-11 Later, transesterification of Si-substituted tri alkoxys il anes was widely and successfull y used for R, RI = Me, R' = H (9); R, RI = -CH=:CHr R' = H (10), R = the synthesis of I-vinylsil atranes and vari ous I-su bsti CH=CH" RI = Ph, R' = S iM e~ (11) tuted sil atranes2.".xo.x ,. It was observed that besides vin yl group, if phenyl group was present at the silicon of th e cycli c ether, mi gration of phenyl group took pl ace under the influence (RO)3SiCH=CH2 + N(CH CHPH\ ~ 2 X3 2,3 4 of base giving ri se to product of sil atrane structu res .
C H ~C H , OH N(CH,CH,O),SiCH=CH2 + 3ROH - - . S i (OC H , C H ,), NC H , C H ,oSiMc ~ ----~ 1 Ph/ - P h S i Me ~
R =: Me (2), R = Et (3) N(CH,CH,o),SiCH:=CH, NASIM & VENKATARAMANI: VINYLSILATRANES 267
The scope of trans esterification reaction is not lim 1- Vinyl-3-(2-vinyloxyethoxymethyl)silatrane (28) ited and the synthesis of various I-v inylsilatranes hav was obtained in almost quantitative yield by the acti on ing different substituents in the atrane fragment as well of compound 3 with N-[2-hydroxy-2-(2-vinyloxy as at alpha and beta carbon atoms of vinyl group have ethoxymethyl) ethylbis(2-hydrox yethyl ) amine] (27) at X7 been accomplished usin g this methodology. Thus, I-(a 20-40"C in the absence of catalyst • chloro-, ~-chloro- , ex, ~-dichloro- and ~ , ~ ' di c hlor o) X4 vinylsilatranes were obtained in 85-95 per cent yi eld s HN (CH,CH,OH), + CH,- CH-CH,OC H,CH,OC H=CH, by reacting the corresponding vinyltrialkoxysilanes with - -- ' 0 1 26 - -- compound 4.
(RO\ SiC(X) = C (XI) (Xl ) + N ( CH I C HPH » ) ~ __-+. N"" (CH,CH,OH), N(CH lCHP »)SiC(X)=C(X I)( Xl) 3 ' CH;t HOH 12-15 CH,OCH,CH,OCH=CH, 27 X = XI= H, Xl= CI (93 per cent) (12); X = CI, XI = XI = H (90 per cent) (13); X= XI= CI , X~ H (92 per cent ) (14); X = H, XI = Xl = CI (85 per cent ) (15) Lower yields were observed in the case of I-(beta phenyl- and beta silyl)v inylsilatranesxs. A seri es of I-vinylsil atranes which were C I (RO»SiCH=CHR + N(CH2C HP H\ ~ trifluoromethyl substituted in the 3-position of atrane fragment were prepared in 45-99 per cent yields by N(CH2CH20»SiCH=CHRI + 3ROH transesterification of the corresponding vinyltrialkoxy 16-18 silanes with tri s(2-oxyalkyl)amines. The reacti on was R' = Ph (70.6 per cent) (16), SiMc) (83 per cent) (17), SiMelh carried out without solvent in the presence of 10 per cent (70.8 per cent) (18) methanolic solution of sodium m e thoxide xx.~' . In the case of I-vinylsil atranes containing sub ACH,CI J,OH), stituents in the atrane fragment, difficulty arises in ob (RO),SiCH=CH, + N taining trialkanolamines with desired structure. The re ~ r;: HOIl 2 or 3 R'R' R' ac tion conditions and yield of 3-sub stituted-l 29-32 vinylsilatranes mainly depend upon the structure of / Cll,CH,O, trialkanolamine used. Thus, 3-chloromethyl-l ---+. N-{;H,CH,O - SiCH=CII, + JROH ;>C-r:HO"""- vinylsilatrane (22) was obtained in 25 per cent yi eld us Iii R2 h? Xfi 33-36 ing sodium rnethox ide as catalyst . R' = R' = H. R' = CH,CF, (33); R'= R'= H, R' - CH,C,!', (34); R' ~ R' = Me, R' - H (35); R' - Et, R' - R' = H (36) ...-oCH,CH,Q}[ (EtO),SiCH=CH, HN(CH,CH,oH), + ~, -J:HCH, CI --+ ~H,CH,Q}( ([ CH,<;HOH A new class of (4S)-( -)-I-vinylsilatrane-4-carboxy 19 20 21 t~J,CI / {;H,CH,~ . li c ac id (39) has been synthesized in 72 per cent yield by ~ C~J,CH , O...... - SiCH=CH, + JEtOH a-r,p·(O the transesterification of compound 3 with L- N, N- bi s(2- CH,CI hydroxyethyl)serine (37) in the presence of pyridine. 22 (3R,4S)-( -)-1- Vinyl -3-methyl silatrane-4-carboxy li c ac id 3-Phenyl-I-vinylsilatrane (25) was obtained In (40) was similarly prepared in 67 .5 per cent yield by fairly hi gh yield (79 per cent) under analogous condi reactin g with L-N, N-bis(2-hydroxy-ethyl)threonine'!2 (38). tionsxfi .
/ (CH,CH,OH), /(CH,CH,OI-l), (EtO),SiCH=CH, H:C°~H (EtOj,SiCH=CH, + N ---+ ! HN(CH,CH,OH), + ~H - Ph ----+ N" Q:!' "P'I-r:HOH R Si o CH,CHOH 3 I Hoot R GI' 23 24 Ph CH=CH, ...... - CH,CII,O" 37,38 39, 40 N--CH,CH,O -jSiCIl=CH, + JEtOH R = H (37), (39); CH, (38), (40) 'CH,~HV Ph 25 In the absence of pyridine, the transesterifi cati on can barely proceed under th e usual reaction conditi ons. 268 J SCI IND RES VOL.59 APRIL 2000
This is probably due to the existence of th e Zwitterionic more than 90 per cent. form of the dihydroxy-ethylated amino acid and the I/x (RSiHO), + ( HOCH 2 CH 1 )) N ~ RSi (OCH1CH 1))N + Hp + H2 protonated amine being unable to form the Si·N dative R = ·CH = CH bond. It seems most likely that the catalytic mechanism 2 of pyridine in thi s reaction is to restore the lone-pair of In the reaction of compound 4 with electrons of the nitrogen and thus facilitate the forma polyvinylhydrosiloxane the first to react was the Si-H tion of the transannular Si-N dative bond and the conse bond which results in the liberation of hydrogen. This quent silatrane ring. On the other hand, pyridine can also was followed by the cleavage of the siloxane bond with increase the mi scibility of the reactants in the reactionn . consequent water formation. It was therefore not the Till now, we have seen that the main synthetic ap completion of hydrogen evolution, but the termination proach to th e I-vinylsilatranes has been th e of water formation that indicates the end of the react ion. transesterification of vinyltrialkoxysilanes with Compound 1 was also obtained by the reaction of tri alkanolamines. organosilicon compounds, i.e., silicones or azasilicones There is another easily accessible vinylsilane hav having Ph and vinyl group at silicon atom with com in g Si-O bond and which has been successfully investi pound 4 or its tri s trimethylsil yl ether or cycli c sily l ether%. gated for obtaining compound 1, is vinyltriacetoxysilane (41). Thus, compounds 1 and 6 were obtained in almost CH, ~ CH /OCH,CH" qu antitative and 82 per cent yields, respectively by the / 'si 0 I N(CH,CI-!,OR), Ph 'oCH,nr( reaction of compound 41 with compound 4 or 5 using 43 4,44 chloroform as solvent at O"C, followed by the continu R ~ H (4), SiM", (44). ous removal of acetic acid formed during course of the CH, ~ CH, ( OCI!,CH, /5 _/,X + reaction with toluene. No catalyst was required for com Ph OC H,CH1 YJ pletion of the reaction . .43, 45 9,45 X ~ 0 (43), NMe (45); R - H (9), SiMe, (46) (CH ,COO\ SiCH=CHI + 4 or 5 ~ 1 or 6 + 3CH,COO H 41 It is seen from the above reactions that compou nd s ZeichanY4 and Voronkov el of. 12.Y5 utilised the more 2, 3 and 41 or polyvinylsesqui siloxanes and easil y accessible vinyltrichlorosilane (42) as the start polysiloxanoles were used as starting material s in th e in g materials in place of compounds 2 or 3 and 41 for tran sesterification reaction which were themselves ob the sy nthes is of compound 1. This method is essentially tained by alcoholysis , acetolysis or hydrolysis of com based on the reaction of triethanolamine with hydrol y pound 42, respectively. sis products of comp ound 42, i.e., polyvinyl Recentl y, another method was established Y7 for the ),' . sesqui sil oxane, (RSiO u polyvinylsiloxanol, [RSi I 5 (OH)2 ]X (Y=O-I .S) and polyvinylhydrosil oxane, synthesis of compound 1 in which compound 42 was y y . (RSiHO)" in the presence of catalytic amount of metal used directly as a starting materi al. In this method , com hydrox ide l2 (preferably KOH ). pound 42 was reacted with the read il y accessible tri s(2- trimethylsiloxyethyl)amineYX (44) at 140-\ SO"C with the concomitant removal of (CHJ)JSiCI to gi ve compound 1 (RSiO,)y + (HOCHzCH 2),N ~ N(CH1CHP),SiR + H20 in 80 per ceilt yield. l/x [RSiO, ;./OH)z)x + (HOCH ICHI )) N ~ ] + 3Me,SiCi N(CH CHP))SiR + ( I.S+Y)HP 2 42 44 R = ·CH=CH1 A new conveni ent metal exchange meth od for the Water fomled during course of the reacti on was synthesis of compound 1 has been investigated, re gradually eliminated by azeotropic distillation with a centlyYY. In this method, compound 3 was reacted with suitable inert solvent. The fo rmation of compound 1 and boratrane in th e presence of catalyst usin g DMF at hi gh phenylsilatrane from the corresponding silanes with com temperature. pound 4 is considerably faster (0.5 - I.Sh) unlike the CH =CHSi(OEt\ + B(OCH CH ))N ~ CH z=CHSi (OCHzCH ), alkyl derivatives which took anywhere from 4··8 h for its 2 2 2 z formation. The yield of compound 1 was al so usually 3 1 NASIM & VENKATARAMANI: VINYLSILATRANES 269
The reactivity of RSi(OEt)J decreases in the fol simply heating the reactants (I OO"C, 8h) in the absence lowing order: R= Ph> 2-furyl > vinyl> Me - 2-thienyl of a catalyst 1m. > chloromethyl. /Ph I-Vinylsilatrane-3, 7, 10-trione (47) was synthe N(CH2CH,OhSiC~Ph + R,MH ---+ N(CH,CH,OhsiC=C\. sized almost in quantitative yield by reacting compound MR, 56 57-61 62-65 41 with aminotriacetic acid in vacuum at 90-1 OO"C in R,M=Et,Si (25 per cent) (62); (EtO),Si (49 per cent) (63); Et,Ge (96 per cent) (64); EI,Sn the absence of solvent ()(). ' (95 per cent) (65)
CH 1=CHSi(OCOCH)) + (HOCOCH1\N ~ CH1=CHSi(OCOCH1»)N In the above reactions the hydros il y latio n/ 47 hydrometallation takes place, regiospecifically, to yield the beta adducts in contrast to the formation of both al Similarly, l-vinylsilatrane-3, 7-dione (48) and 1- pha and beta adducts in the hydrometallation of acety vinylsilatrane-3-one (49) were synthesized in 64 per cent lenes not having a silatranyl moiety )()4. yield by allowing the mixture of compound 3 with N-(2- hydroxyethyl)-aminoacetic acid tri s trimethylsilyl or N,N 3 Properties of 1-Vinylsilatranes bis(hydroxyethyl)aminoacetic acid tris trimethyl-silyl The electronic structure of I-substituted sil atranes derivatives to stand at room temperature for 2-3 h or have been earlier investigated 2 . '1.I(J5 - 'o~. However the heating the mixture at 40-50"C using DMF as solvent)()'. chemical reactivity of these compounds has been stud / (CH,COOSiMe,)" ied to a lesser extent. This is particularly applicable to CH,=CHSi(OEt), + N -7 - ...... 3 (C H,CH ,OSiMe,),." I-vinylsilatranes. The presence of carbon-carbon dou ble bond in the molecule makes it amenable to a wide _ (C H,COO)"...... variety of chemical transformations. n=3 (47), n=2 (48), n= 1 (49 ) N SiCH=CH, - "" The 'H, DC, t5N and 2~ Si NMR spectral data ob N(CH1CHP»)SiCH=CH1 + 3Hp ~ tained for compound 47 indicate that an increase in th e N(CH 1CHPH\ + (HO»)SiCH=CH number of carbonyl groups in the atrane framework en 1 hances charge transfer along the donor-acceptor N-Si bond. Because of the prominent electron-acceptor prop The course of hydrolysis of compound 1 and I-Si erties of the central atom, the atranetrione (47) tend to substituted si latranes were followed with the help ofUV bind electron-donor solvent, i.e., DMF. This is accom spectra (increase of absorption intensity,(n.sigma*l due to panied by an increase in the coordination number of sili the participation of electron pair of N-atom in the cleav con in compound 47-DMF complex, increasing it to six 101 age product formed during the course of hydrolysis) in neutral medium (buffer KH PO/ N~HP0 4' 2S"C, pH A series of trans beta substituted I-viny lsi latranes 2 were obtained by hydrosilylation of ethynylsilatrane in 7.15)"°. a regiospecific mannerl 02 It was also found that I-alkenylsilatranes under these conditions are hydrolytically less stable as com N(nhCH20hS\ /H pared to alkylsilatranes, RSi(OCH,_ CH2 ) 3 N, (R= i-PI' > N(CH~H20hSic."CH + R.Sll\feJ~H -- / c=c CH2CI > Me> CH2=CH). Based on the available data, H \SiRnMe J ~ the authors proposed a possible reaction mechanism of 50 51-55 R=Ph, n = 1 (50); R=1hienyt, n= 1 (51), R=Ph, n =2 (52); R=thienyl, n=2 (53), R=Ph, n=3 the hydrolysis. The initial formation of a four member (54); R=thienyl, 0=3 (55) intermediate by coordination of the oxygen atom of wa ter with silicon and hydrogen bonding with the oxygen Likewise, l-(beta phenylethynyl)silatrane was read of the atrane skeleton, followed by a slow cleavage of ily hydrometallated with group IVB metal hydrides by atrane fragment (Scheme 1). 270 J SCI IND RES VOL.59 APRIL 2000 N(CH,CH,OhSiCH=CH, + AgF --+ CH,=CHAg(,AgF) + N(CH,CH,O), SiF I (r) \ 67 . + 11,0----+ (x · ?) \ (Yellowrm7 R H20 (black) ·Ag + CH,=CH·CH=GI, N(CH,CH,OH), + . (HO)JSiR R=-CH=C~ Scheme 2 - Synthesis of tluorosilatrall c Scheme 1- Mechanism or hydrolysis or sil alranes formed which further decomposes giving ri se to Ag and butadi ene according to the Scheme 2 proposed by Mullar Similarly, alcoholysis of compound 1 in acidic el m . l al. The primary product seems to be flu orosil atrane medium cleaved the atrane fragment I I. (67). ROHlHCI CH,=CHSi(OCH,CH,).• N ----+. HCI. N(CI-J,CH,OH), + (RO)JSiCH=CH, Transfer of vi nyl group from sil icon atom resu lted 1 R~Mc .E t in the cleavage reacti on of compound 1 by aqueous so lution of heavy metal salts i.e. Pb and Hg. The process However, it is possible to isolate the hydrochloride of occurs in the same way as given in Scheme 2. Muller compound 6 with th e retention of th e silatrane ring by and Frey l1 4 established this transformation in the pres passing dry hydrogen chloride in chloroform solution at ence of H20 and ammonium flu oride. ll2 room temperature or even below . I + HgCI, + NH,F + H,O ---> m '.N(CH,CH,OH), + CLHgCH~CH , + NH,CI + SiO, CI-I 1=CI-ISi(OMeCI-ICH1)lN -+ HCI N(CI-IFHMcO\ SiCI-I=Cl-I l &9 per cent 6 I + Pb(OAc),+ NI-LF + H,O --+ CII,COOH.N(CH,CH,OH), + F,Pb(CH=CH,), 65 per cent The hydrochl oride is stable in acetonitrile but hy + FPb(CH=CH,h + Ni-l,OCOCH, + SiO, drolysis in water immedi a te ly gives tris(2- 35 per cent oxypropyl)amine hydrochloride and polyvinylsesqui • The facile transfer of vinyl group is due to the fo r oxane, CH =CHSiOI 5 2 mation of an intermed iate, ammon ium pentafluoro 3.2 Interaction of 1- Vinylsilatralles with Compounds vi nylsilicate, which is acti vely involved in the exchange Having Element-Halogen Bond reacti on with the heavy metal salts". The interaction of compound 1 with compounds N(CHF HP),SiCH=CH2+ 3Hp-+ containing element - halogen bond (where E-X = metal N(CH1CH10 H») + (1-I0 ),SiCH=CI-I1 halides e.g. HgCI , AgF, SbF and ICI , sulpheny l chlo 2 J (HO»)SiCI-I=Cl-I l + 5N H4F -+ ride, polyhaloalkanes, N,N-dichloroaryl sulphamides etc) (N H4)/CH1=C I-IS iF\) + 3NHpl-l mainl y depends upon the nature of these bonds and th e (NH)/CH1=CHSiF;) + M · x -+ M ·· CI-I =CH + (NH,\SiF;X experimental conditions employed. 1 Unlike hydrolysis and alcoholysis the reaction of compound 1 with antimony trifluoride proceeds with However, Nies et al. 115 observed that the epical Si metal transfer to retain the atrane skeleton and cleavage C bond of compound 1 is extraordinarily susceptible to of Si-O bond g iving rise to vinyltrifluorosilane and the direct electrophilic attack by Hg(Il) in acetone-d() to stibatrane IIJ. form l-chlorQ- silatrane (68) and vinyl mercury chloride. CH =CHSi(OCH CH \ N + HgCI -+ N(CHzCHP\ SiCI-I=CH l + SbF) -+ 2 2 2 2 N(CH CH,G),SiCI + ClHgCH=CH? 2 - . - CH2=CHSiF) + Sb(OCH1CH 1\N 68 66 An important point to be noted here is that there is Muller suggested : IJ that this type of exchange re no need for prior hydrolysis and conversion of compound action is due to the increased tendency of Si towards the 1 to ammoniumpentafluorovinylsilicate. Relative rate formation of strong Si-F bond. measurements of the reaction showed that compound 1 Silver fluoride reacts with compound 1 with cleav is more active than I-aryl-, and I-alkyl substituted age of Si-C bond. As a result, an unstable vinylsilver is sil atranes in this kind of transformation. NASIM & VENKATARAMANI: VINYLSILATRANES 271 It is suggested that vinyl group initially forms 7t and formylacetonate of trivalent chromium and cobalt llX . complex with HgCI2, which effectively eliminates the steric hindrance otherwise posed by the groups. Once - 45·C held in close proximity to Si-C bond, the Hg(II) now has much greater probability of successfully attacking in a manner similar to aliphatic ;·eaction. The silatranyl group in l-organylsilatranes possesses a strong electron donat ing effect lO4 and readily undergoes electrophilic Si-halo genation through the reaction of heavy metal hal ides 113. 11 5 The Si-C bond of I-vinylsilatrane is cleaved by bromine or iodine chloride to yield I-bromosi latrane or compound R=Mc; M=Cr (ill) - 36 pcr cent (71), REM.; M=Co (In) - 30 per cent (72). R=H; M= Cr(m) - 15 per cent (73) 68, respectively. In the presence of diethylether or THF and under the action of dioxane bromide, 1- bromosilatrane is formed together with l-(omega The reaction of compound 1 with dialkylphos haloalkoxy)silatranes 11 6. phoryl- (74) and dialkylthiophosphorylsulfenyl-chloride (75) was more complex II~. It was shown that apart from N(ClhCH,O),Si - Y + RX the expected formation of compound 68 and S XY=Br,. Y=Br (25 per cent), RX=CHFCHBr; XY=!CI, Y=CI (19 per cent), RX=CHFCm vinylthiophosphate, CH2=CHSP(O)(OR)2 (76) or N(CH, CH 2 0h Si~H =CH' i · ·C) .Dr, -- N(C H,cH~OhSiDr (16-4 per cenl) viny ldithiophos-phate, CH,=CHSP(S)(OR)? (77), vinylsulphides (78 and 79) h~vin g silatranyl group in N(CH,CH,O),SiOCH,CH,OCH,CH,Br (1 4·6 per cent) the molecule was also isolated (Scheme 3). Two parallel The reaction of l-vinylsilatrane with Br2 or ICI in processes occur simultaneously after the initial add uct dichloromethane or chlroform proceeds smoothly and formation with the -C=C- bond of compound 1 at -SO"C even at - SO"C involves cleavage liO of the Si-C bond of (i) beta scission and (ii) The migration of silatranyl group compound 1. during the formation of a quasiphosphonium intennedi Similar case was observed in th e reac ti on of com ate. Kuteerev et ai. II~ suggested that this intermediate pound 1 with the electrophilic reagents having S-Cl could be the precursors of the reaction products whi ch bond "?, i.e., phenylsulphenylchloride (69). However, predominates in the isolation of the mixture of products. , unlike HgCI 2 phenyl-sulphenylchloride adds to com -50"'C pound 1 with the formation of a stable adduct, 1-[2- N(CII,CH,O),SiCH=CI!, ,. (RO),P(X)SCl ~ chloro-( l-thiophenyl)]ethylsilatrane (70) at very low tem 74,75 perature 117 . ~ N(CH,ClhO),SiyH-fH, ~ rN (CH 'CH,o)' S! -CIH ; . ~'l (Ro},p(X)s CI ~ 1" J N(CH,CH,o),SiCI I=CH, + PhSCI , N(CH,CH,O),SifHyHl 69 70 PhS CI R00R CH1] _ >_ -_IO_' C_ N(CH'CH'O),[~~th" ' N(CH,CH,O),SiCI + PhSCH=CH, 68 I a.r CI,\!, ~ C(CH,CH,o)'Si -~ OR] N(CH,CII,O),SiCI I It was proved by IH NMR that adduct formation 68 takes place only in mild condition (- IO"C). At higher CH, - CH- / ORJ IXI (RO}'pSCH = CH, temperature, it undergoes fragmentation (beta fission) bl-RCt 76,77 via cyclic episulphonium intermediate resulting in the N(CH,CH,O), Si - x" /p X - O(76), X=S (77) formation of compound 68 and phenylvinylsulphide. It CHi"CH~/\R is wellknown in organoelement compounds that in a bond 78, 79 sequence like M-C-C-Y, beta fragmentation takes place X - 0 , R- CH" i-C,H, (78), X- S, R= i-C,H, (79) because of high electron donor of silatranyl group. An analogous reaction proceeds by the interaction of compound 1 with sulphenylchloride acetylacetonate Scheme 3 - Addition of dialkylphosphoryl- and dialkylthiophosphosulfenylchloride to J-v inylsilalrane 272 J SCI IND RES VOL.59 APRIL 2000 , In contrast to HgCI 2 phenylsulphenylchloride, sulpheny Ichloride acety lacetonate/forrny I-acetonate of Table I - Addition of RH,'X to I -yinylsi latrane tri valent chromium and cobalt, dialkylphosphoryl- and Reaction Condition Yield of adducls, d ia Iky I th iophos-phoryl su Ipheny Ich lorides, N,N per cent dichloroaryl sulphamidesl ~o, ArS0 NCI add s to com 2 2 (PhCOO)P, CHCI), S5.2 pound 1. sealed tube 6 h, SO"C ArSO NCI + CH =CHSi(OCH CH »)N --7 z 2 1 1 2 F,C- I Scattered sun light, CCI~ +CHCI,. 94.5 ArSOlNCICHzCHCISi (OCHzCHZl)N sea led tube, 30 11 , room temperature Ar= Ph , p-CIC H , p-CH)C H4 6 4 6 UV, CHCI), sea led tube, 3 11 , 9S. 1 In the presence of moisture the above addition prod room temperature uct converted to corresponding addition product, ArS02NHCH2CHCISi(OCH2CH2),N (ref. 120). In a 1:2 molar ratio of reactants the reaction in However, at -78" C, lBuLi adds only to th e C=C vo lves two chlorine atoms of N,N-dichloroaryl bond with no attack on the silatrane rin g. sul phamides. The yields of the products are nearly quan -78"e titative l20 . N(CHzCHP\ Si CH=CHz + 'B uLi ~ ArSO CI + 2CH =CHSi(OCH CH ») --7 z 2 z z z 'BuCHzCHzSi(OCHzC H) ,N ( I R per ce nt ) ArS01N[CHzCHCISi(OCHP1l »)N 12 84 45 64 However, Nasim et al. . have established that The addition of C-X (X=Br, I, F) to compound 1 compounds 1 and 6 react exothermally at room tempera was found to be less reactive. Reacti on was initiated by ture with electrophilic reagent, i.e., N-bromosuccinimide benzoyl peroxide or photochemically and adducts hav in the presence of small excess of water leading to the ing perhalogenalkyl group in the termin al carbon were formation of corresponding bromohydrin s (80 and 81 ), isolated in very good to excellent yields l22( Table I). respectively, in more than 80 per cent yields. N(CHzCHP \ SiCH=CHz + R"" X NBSIH20 N(C H z C HP ) , S i CH(X)-CH ~ RI"" N(CH2CHRO),SiCH=CH2 I N(Cl-hCHRO),SiClfBrCH20H 80,81 85-87 R=H (8\ per cent)(80); Me (8\ per cent)(81) R"·"=CI,C, X=Br (85), R"·" = F)C, X=I (86), RH,' =F C), X=I (87) 7 Th is was somewhat surprising since it is known In a recent work by Voronkov el at. 123 and Geyer ef that reaction of N-bromosuccinimide with 1- al. l2~ the photochemical addition oftrifluoroiodomethane organyl silatranes, e.g., arylsilatranes, in methanol or in to compounds 1 and 42 have been desc ribed. The addi dichloromethane, affords onl y l-bromos il at ranesI 21. tion of CF}I to compound 1 proceeded smoothly to give The reaction of compound 1 with alkali earth met 79 per cent of the addition product in 102 h, whereas als, e.g., "BuLi in hexane so lution has been r e ported~ Y . compound 42 gave a poor yield of the adduct (35 per Wi th "BuLi, there was simultaneous substitution of Si cent) and took much longer reaction time ( 10 d). bonds and addition to the C=C bond. ° Yoronkov el al. 123 established th at the additi on of (CHF HP»)SiCH=CHz + "BuLi --7 pol yfluoroiodoalkanes to compound 1 and its C-subst i "BuCH CH Si (OCH CH ),N tuted derivatives gave the corresponding 1- (2- z z z 2 perfluoroorganyl- I -iodoethyl)-silatranes. ( I 7 per cent) 82 RI + CH/=CHSi(OMeCHCHz),,(OCHzCHz),.,,--7 + RCHzCHISi(OMeCHCHz),.(OCHzCHzl,."N nBuCH CH SiBu} 2 2 8S-97 R=CF), n=O (9 5 per cen t)(88); R=Cl , n=O (9 7 per cel1l )(89): (30 per cent) 7 83 , . R=Cl7 n= I (78 per cent) (90): R=Cl7 n=3 (86 per NASIM & VENKATARAMANI: VINYLSILATRANES 273 Table 2 - Addition of Cl 1CCOOMe to I-vinylsilatrane in presence of different initiators for 4 h Experiment Peroxide/metal Nucleophilic t Yield no. complex initiator initiator (uC) (per cent) I BZP2 95 65 2 Fe(CO), CH1COOK 120 43 3 Fe(CO), DMF 120 41 4 Fe(CO), CH1CN 120 64 5 Fe(CO), HMPT 120 72 6 Fe(CO), 140 37 7 Fe(CO), 140 42 8 Mo(CO)r. 140 39 cent)(91); R=H(CF)4' n=O (100 per cent)(92); Fe(CO), + DMF, Fe(CO), + CH,CN, Fe(CO), + HMPT R=CF (CF ) 3' n=O (100 per cent)(93); R=H(CF ) (" n=O gave the adduct - methylester of 2,2,4-trichloro-4- 3 2 2 (79 per cent)(94); R=C F , n=O (91 per cent)(95); silatranylbutyric acid (99) in 37-72 per cent yields de 6 n pending upon the reaction conditions and catalyst em R=H(CF )x' n=O (100 per cent)(96); R=CF (CF )7' n=O 2 3 2 ployed65 (Table 2). (100 per cent)(97) Reaction proceeded slowly (60-120 h) in the pres CCI,COOMe, N(CH,CH,O),SiCH=CH, N(CH, CH,O),Sif~CH,CCJ,COOMe ence of scattered light but under UV-irradiation the re 98 99 action completed in 2-3 h. Yields of the adducts were 78-100 per cent. In all the cases only the simple addition product The reaction of compound 1 with various reagents was formed unlike the reaction of compound 98 with have been studied, e.g., hydrometallation2. ' 2, . 127 which is trimethylvinylsilane, which gave both the addition prod discussed subsequently and radical initiated addition of uct and the lactone depending on the single or combina 12x species containing N-CI, S-H, P-H, C-H, C-Br or C-I tion of initiators employed • which occur with retention of the Si-C bond but reac The exclusive formation of the addition products tions with electrophile, 69 will give compound 68 with only is ascribed to the ability of atrane fragment pl ay in g cleavage of a silicon - carbon bond 117 . But radical initi the role of nucleophilic initiator itself. ated addition of species containing C-CI bond to com pound 1 has not been reported in the literature prior to 3.3 Interaction of 1- Vinylsilatranes with Compounds the work of Kamysheva et a/. 65 . This is because of the having Element-Hydrogen Bond less reactivity of the monomer under radical condition Only two types of compounds with E-H bond, i.e., and that molecular mass of chi oro alkyl aryl polymeriza Hp and alcohol, react with compound 1 with cleavage tion slow down in the presence of silicon containing spe of atrane fragment. All other compounds with element ciesI2X.129. hydrogen (E-H), i.e., C_H I27, Si_H2. 125. 127. 13o.m, Ge-H I27, It was established by Kamysheva et al.65 that the Sn-H I27 , P-H I33 and S_H2.X2 give rise to more or less sta addition of C-CI species to the carbon-carbon double ble adduct of compound 1. bond of compound 1 occurs with retention of the The addition of C-H bond of chloroform to com silatranyl fragment under conditions of peroxide and pound 1 initiated by benzoyl peroxide took place on heat metal complex initiators. Compound 1 does not react ing the reaction mixture at 100"C for I h in a sealed with methyltrichloroacetate (98) in the absence of a cata tube 127 . lyst. The reaction of compound 1 with compound 98 in N(CH2CHP)JSiCH=CH2 + H-CCI) ---7 the presence of peroxides, i.e., benzoyl peroxide or metal complex initiator, Fe(CO\, MO(CO)6 or in certain cases N(CH2CHP»)SiCH lCH 2CCI ) using nucleophilic initiator, i.e. , Fe(CO), CH COOK, + 3 100 274 J SCI IND RES VOL.59 APRIL 2000 On prolonged heating (6 h) at 80"C th e addu ct for di adduct with compound 1. The hydrosily lati on reactions mation was not observed which led to the use of chloro were catalysed by ch loropl atini c acid in THF"I. fonn as solvent in the reaction oftrichl orobromomethane with compound 1 (Table I). Me'HS> N(CfI,CH'OJ,SiC . f1 ' CHz.Me ' Si~ 2N(CH,CH,O),SiCH=CH, + S -- Y Hydrosilylation of compound 1 has been studied Me,HS' N(CH,GH,O),SiCH,CH,M.,Si in detail with silicon hydrides hav ing alkyl, alkoxy, aryl , heteroaryl substituents at the si li con atom 127 . Irrespec Under analogous conditions but at low tempera ti ve of hydro sil ane structure and experimental conditions ture the hydrogermyl at ion of compound 1 proceeded employed, in all cases the adducts were obtained in hi gh smoothly usin g Rhacac(CO)2 as catalyst 127 . yields. Only ~-addu c t s were obtained as a resu lt of th e N(CI-I1CI-I P))SiCI-I=CI-I1+ I-IGeEt ) ~ addition of silyl group at the terminal carbon atom of N(CI-I1CHP))SiCH1CI-I 1GcEt) vinyl group of compound 1. ( 100 per cen t ) N(CHFHP))SiCH=CH + R)SiH ~ 1 115 N(CH1CHP),SiCHF H1SiR, The corresponding hydrostann ylation reaction of Nasim e t a l .12S.126 have reported a seri es of compounds 1 and 6 proceeded in th e absence of a cata hydrosilylated products, 2-silylethylsilatranes, in yields ly stl27 . ran gin g from 75 to 90 per cent by refl uxing the reacti on N(CI-I1CI-I RO\SiCH=CI-I + I-ISn Bu, ~ mixture in benzene for 4-5 h in the presence of HltCIr/ 1 i-PrOH. N(CI-I1CI-IRO))SiCI-I 1CH1SnBu) 116-117 N(CH CHR 0 ))SiCH=CH + R1M eS iH 2 1 1 R=I-I (7 1 [ler cent) (116); M e (74 per cent) (117) N(CH1CHR10))SiCI-I1CI-I 1SiMcR 1 101-109 Hydrometallation reacti on was not observed if the vinyl group of compound 1 was substi tuted by styryl R,=H, Me; R=Et (80 per cent) (101), n-Pr (90 ' er cent) group . However, th e correspondi ng ethy nyl derivative, (102), n-Bu (89 percent) (103), Allyl (86 percent) (104), N(CH 2 CH,o) _ ,., SiC=CPh, was readily hyd rometallated Ph (75 per cent) (lOS), p-CIC r> H4(79 per cent) (106), p with R } MH at 100"C for 8 h with the exclusive forma FC H (77 per cent) (107), p-MeC 6 H ~ (82 per cent) (108), 6 4 tion of beta add uct in 96 per cent yield IO}. C H CH (77 per cent) (109) (, S 2 Hydrosilylation of compound 1 with The reaction of 2-furyl- and 2-thi enylsil anes with o li go meth ylh yd rosiloxanes having te rminal 2 111l compound 1 evidentl y was more active . • It bas been trimethylsilyl groups in the presence of chloroplatinic observed that ease of addition was dependent upon the ac id afforded the corresponding oli gomers hav ing mo number of furyl and/or thienyl groups present in the lec ul ar weights of 1000 and 2000 which can be used as hydrosilanes. Thus, tri s(2-furyl) silane added with greater surface active compounds l.l2 . ease (room temperature) th an dimethyl (2-furyl) silane (needed heating). N(CH,CH,O),SiCH=CH, + R"SiH --->. N(Cll,CH,OJ,SiCH,CI l,SiR" 110-114 ~ N(C I-I1CI-I P),SiCH1CH1SiMel(OSiMel)n R,=Me,( 0 )(95 pcr cent) (110), Me (0 )'(89.5 per cent) ( III) ,On OSiMe1C I-I1CI-I 1Si (OCI-I 1CI-I ),N 118 (82 per cent) (112), M~ (0 )(82 per cent) (113), Me (!i..) h (88 pcr cent) The addition of P-H bondto compound 1 is usu ally initiated by UV-irradiation. However, compound 1 (114) adds with dialkylphosphites more readily in th e pres 111 ence of sodium alkox ide than under UV-irradiation . Likewise, bis(dimethylsilyl)th iophene gdve a Introduction of metlJyl groups at 3, 7 and 10 positions of NASIM & VENKATARAMANI: VINYLSILATRANES 27 5 the silatrane skeleton markedly activates the double bond, 133 N(CH,CHMeO).(CH,cH,O)' ..5iCH=CH, + MeOOCCH,SH thus increasing the yield of the adducts , Thus, com pound 1 fails to react with dipropylphosphite upon UV ---+ N(CH,CHMeO),,(CH,CH,O),~SiCH,CH,SCH,cOOMc 133,134 irradiation, Whereas compound 6 easily reacts with dime r>=1 (85 per cent) (133); n=3 (90 per cent) (134) thyl-, diethyl- and dipropylphosphites to give the cor N(CH,CHMeO).(CH,cH,O), ~SiC H=CH, + RgSH responding addition products in 96.4 per cent, 92,3 per - N (CH ,C HMeO).(C H , CH,O),~SiCH,C H ,SC(O)R cent, 68,1 per cent yields, respectively, 135·138 N(CHF HRO)JSiCH=CHl + (RIO)l(O)H ~ 0=0, R=Me(lOh, 50 per ccot) (135), n=3, R=Mc (611, 85 per cent) (136), n=D, R=Pb ( 1011, N(CHICHRO)J SiCHICHl(O)(OR 1) 1 88 per cent) (137), n=3, R=Ph (6h, 85 per cent) (138) 119-122 One more class of compounds having S-H bond is R=H, R'=Me (60,S per cent) (119), R=Me, R '=Me (96.4 dithioacid of phosphorus, which easily adds to the dou per cent) (120), R=Me, R '=Et (92,3 per cent) (121), bl e bond of compound 1 to give the beta adducts" ·} . R=Me, R '=Pr (68, 1 per cent) (122) 20°C, 3 d With radical initiator (AIBN), diphenylphosphine N(CH1CH20 )3SiCH=CH2 + (RO):zll(S)SH forms beta adduct with compound 1. In the case of C --+ N(CH2CH20MiCH2CH2SP(S)(OR)2 139,140 methyl derivatives the reacti on may occur without ini R=Me (75 per cent) (139), i-Pr (71 .3 per cent) (140) tiators 133 , (CHICHMeO)..{C HICHP)J,nS iCH=CH1+ PhlH ~ 3.4 Other Reactions with /-Vin yl- and /-Vinyl-3, 7, /0- N(CH1CHM eOl" (CHICHP)J.nS iCHICHlPhl Trim ethylsilatranes 123-125 (i) DielsAlder Reaction n=O (80 per cent ) (123), n= 1 (77.6 per cent ) (124), 1- Yinylsil atranes undergoe (2+4)-cyclo addition n=3 (84,8 per cent) (125) reaction with cyclopentadiene and hexachl orocyclo Similarl y, regioselecti ve beta adduct formation pentadiene with great difficulty 134, occurs photochemicall y by thiolation of compound 1. The wide range of compounds havi ng S-H bond in vesti x x gated so far gave vari ous sulfide deri vati vesX2 upon ad 170·180"C N(CH,nI,Oh SiCH-cH, + I I ---+ diti o n of alkanethiols, a lka nedithi o ls, . x x DCx x sil atranylalk ylthiols to compound 1. 141 , 142 143.144 vh , 1·2 h X=H (141 ), X=(,I (142); X=H (80 per cent) (143), C1 (60 pcr cent) (144) N(CI-hCHMcO). (CH,CH,O),..SiCH=Clh + RCH,CII,SH ---~ The adduct, 5-sil atrany l bicyclo(2,2. 1)- hept-2-en -+ N ( CH~HMeO ). (CH~H2Oh.,S i CHlCH 1 SCH~HlR (143) was obtained in 80 per cent yield and was a mi x 126-130 ture of endo and exo isomers as revealed by proton The presence of trimeth oxysilyl group at alpha NMR 134, The reaction of compound 1 with maleic anhy position to the thiol group signi ficantly increases the time dride or maleimide gave a copolymer (MW - 6000) con X2 for thiolation reaction , taining both the s ilatranyl and imido/anhyd rid e functionalities, 0 homopolymerization was observed vh, 3h(m=2), (m: !) under these conditions 135 , N(CH, CHMeO), (CH,CH10),.SiClf=CH, + (MeO»)Si(CH,)"SH ) -+ N(CH1CfIMeO). (CH,CH10 lJ" SiCH1CH,S(Cl b). Si(OMe») o 131,132 rl 600C, IOh N(CH,CH,O),SiCI-I-CH, + ~ 0=2, m=1 (84 per cent)(131); n=O, m=2 (84 per cent) (132) o Thioacetic and thiobenzoic acids were less reac tive among the thi ol groups studied so far. To some ex ----> [N(CH,CH>O)JSib H-CHQJ tent, meth yl ester ofthi oglycoli c acid was more reactive 145, 146 0 m in which acceptor carbonyl group is away from the S-H x ~ o (145), NI 1 (146) L _ .• _1 ~') 276 J SCI IND RES VOL.59 APRIL 2000 (ii) Oxidation oft-Vinyl- and I-Vinyl-3,7,10- Compounds 150 and 151 were also obtained in high Trimethylsilatranes yields by rearrangement of compounds 148 and 149 us 6 It was reported by Hosomi et af. 121 that the Si-C ing triethylbromostannane as a catalyst4 . bond in organosilatranes is cleaved by m 147 Et,SnBr chloroperbenzoic acid (147). But recently Voronkov ef 1,6 --> 148, 149 --- 150, lSI ai.136 investigated the reaction of compound 1 with com pound 147 and it was found that contrary to the reported Anodic oxidation of compound 1 in acetonitrile at Ll7 Si-C cleavagel21 , the reaction of compound 1 with com a graphite electrode has also been reported . Oxidati(;)O potenti al for compound 1 in acetonitri le at a graphite pound 147 in presence of Na2CO] (buffer) yielded, \ silatranyloxirane (148) in quantitative yield. electrode was found to be I.S2Y. Correlati on with Taft (s igma) constant, 15N NMR chemical shifts and 15N - 2 ~ Si coupling constant suggested that the reaction centre was the N-atom. Cation radical of compound 1 was formed 137 during the reacti on . Perbenzoic acid also reacts similarly but the yield (iv) Synthesis of Silatranyl- and 3,'1, 10- oftheoxirane is lower. 3,7,1 0-Trimethylsilatranylox irane Trimethylsilatranylcyclopropanes (149) was synthesized by Nasim ef af. 46 in 83 per cent Before beginning of the work by Nasim et al.66 on yield via the oxidation of the precursor compou nd 6 with cyclopropanation of I-v inyl si latranes, there were only compound 147, as described l36 above for th e prepara two examples of cyclopropylsil atranes reported in the tion of compound 148. literature, i.e., ) -cyclopropyl l3X and 1-(2-chl orocyclo UY propyl)silatranes • These si latranes were sy nthesized N(C~HMeO)JSiCH=CH2 + m·CICJj4C(hOH -+ N(CH2CHMeO)JSi n by the usual meth od of transesteri fication of correspond 6 147 149 \f ing cyclopropyltrimethoxysilanes with triethanolamine. Nasim et al. 66 developed an easy and si mple method (iii) Synthesis of a-silatranylacetaldehydes for the sy nthesis of cyclopropy lsi latranes starting from compound 1 or 6. The cyclopropanati on of the viny l Nasim et al. 45 ha ve developed a route to alph a group in compou nds 1 and 6 by CH2 /Pd(OAc)2 sys sil atranyl acetaldehydes 150, 151, start in g from the read tem has been carried out to afford cyclopropylsil atranes66 il y accessible compounds 1 and 6 (Scheme 4) via (154, 155). muitisteps functional group transformation. CI I,N,,'Pd(OAc), An analogous procedure gave, 2-(3,7, 10- N(CII,CI'lRO),SiCH=oCH, • N(CH,CHROhSi --..:::-7 154, 155 V trimethy l)silatranylacetaldehyde(151) in quantitati ve R=H (1 54); R=Me (155) yield as a mixture of almost equal amounts of the two In the absence of a catalyst, compou nd 1 and CH N diastreomers hav in g different orientations of the methyl 2 2 groups relative to the axial Si-N bond. do not react to form the correspondingilatranyl substi tuted cyclopropanes, even under UV -irradiation. ]n con trast, vi nyltriethoxy-silaneand CH 2 r ad il y undergo a (AcOhSiCH:CH, ----+ N(CH,CllROhSiCH=oCIJ, ..... (I) 2 -3 AcOH 1,6 I ,3-cycloaddition to give the si lyl substituted heterocycle, NBSIH,O i.e., 3-trieth oxysilyl - l-pyrazolene whi ch fa il ed to yield 1,6 N(CH,CJ-lRO),SiCH(Br)Cl hOH ..... (2) 98, 99 the corresponding si latrane due to N2 el imination. Et, SnOMe 98,99 [N(CH,CHRO),SiCH(Br)CH,OSnEt,] ..... (3) - MoOH 152,153 Conclusions t' 152, Is:! N(CH,CliRO),S~Hl ..... (4) - EI,SnBr 148, \49 ) -Vinylsilatranes are excellent synthons capable of 148,149 N(CH,CHRO),SiCH,CHO (5) undergo in g a variety of reactions to provide new ISO, lSI R- H (150), R=Me (lSI) functional ized silatranes via Diels-Alder reaction , epoxidati on, addition, cyclopropanation, halogenation, hydrometall ati on (hydros il ylati on, stanny lat ion and Scheme 4 - Synthesis of silatranylacetaldehydcs via muitistcps germyla-tion ) reactions. The syn th esis of newer and fun ctional group transformation newer si latranes starting from ) -vinylsilatranes would NASIM & VENKATARAMANI: VINYLSILATRANES 277 not be limited and chirality could be generated in the 27 Voronkov MG & Baryshok VP, J Ol"ganomet Chem, 239 (1982) silatrane molecule using enantiopure trialkanolamines. 199. 28 Voronkov MG, Ovchinnikova ZA & Baryshok VP, /zv AN SSR References Ser Khim, (1987) 880. 29 Frye CL, Vincent GA & Finzel WA, JAm Chem Soc, 93 (197 1) Voronkov MG, Topics ill Curr Chem, 84 (1979) I. 6805 . 2 Voronkov MG, Dyakov VM & Kirpichenko SV, J Organomet 30 Parkanyi L, Simon K & Nagy J, Acta Crystallorgr, 83 (1974) Chem, 233 (1982) I. 2328. 3 Gar TK & Mironov VF, Metalloorg Khim, 1 (1988) 260. 3 1 Boer EP, Flynn JJ & Turley JW,.1 Am Chem Soc, 90 (1968) 6973. 4 Chernysheva ON, Gar TK & Mironov VF, Metal/oOl"g Khim, 2 32 Parkanyi L, Nagy J & Simon K, J Organomet Chem, 101 (1975) (1989) 1209. 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