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Taa Be eepayp a xo poyo pea eaoaeaa c 2-e-1,3-ocaoao (co oo: aaaop - Rh2(CH3CO2)4, pe pea 2 aca) Mooe coooe- O xo Teepa- Paco- Coooee e peaea poyo ypa,0C pe mpac- : uc- a : aop : 13 14, % 20 CH2Cl2 0,01 : 1 : 1,5 46 3 : 40 CH2Cl2 0,01 : 1 : 1,5 72 3 : 60 - 0,01 : 1 : 3 95 3 : B peaoo acce cepeooep uc-14 mpac-14 epoa a ocoa e ax CCB (3Jc =2.8 ; 3Jpac =9.5 ) cepe MP 1H. B cepe MP 13C cec cepeooepo uc-14 mpac-ca yepox aoo C(2) C(3) mpac-oepa peyae - -eo aopax aecee aac oee cao oe o cpae c caa aaox aoo uc-oepa (xece c aoo yepoa C(2) C(3) mpac-14 uc-14 cooeceo pa 82.1 .., 48.5 .. 79.5 .., 42.0 ..). pcyce eo eocapoo py o 2 3 ooex a oaao a ocoa a NOE-eo ey caoo cao pooo p aoe C(2) apoaec pooa. Ta, uc-oepe 14 p oye aoa H(2) a pooax eoo oa aaec NOE-e, pa 6.2 %, oop ocycye p oye pooa H(3).

p aoec 2-e-3-oy-1,3-ocaoa 15 c eo po aoycyco co aaox ycox ee mpac-oep eooo pa 4-oy-3-e-1,4-oca-2-apooo co mpac-16 c xoo 48%.

CH(CH3)CH(CH3)CHCHC6HC6H[Rh] N N + N2CHCO2CHO O CHCO2CHCH2Cl2, 400C [Rh]L 48% CH(CH3)CH6 H(2a) N 1 C6HO H3CO2C H(3a) mpac- Opaoae poooo opoa mpac-16 pocxo peyae aa apea o aoy copoa ocaoa 15 c opaoae O-a eo oceye epepypo.

B cepax MP 13C opoa mpac-16 coee ca 82.2 .., 69.4 .., 62.4 .. 67.1 .. cooeceo paea aoa C(2), C(3), C(5) C(6), oope axoc -ooe eepoaoa a, o yaae a pcyce 1,4-ocaooo cpyypoo paea.

B yepx NOESY cepax coee mpac-16 aaec pocc ey pooa apoaecoo oa pooa p yepoo aoe C(7). o yaae a pacooee eo py p yepoo aoe C(3), axoec -ooe aoy aoa oepae epee eocapoapea o c O(1)-C(2) cxooo 2-e-3oy-1,3-ocao 15.

B cepe MP H coee mpac-16 ea ao CCB (3JH(2a)H(3a)=9,1 ) oaae acay opea pooo H(2a) H(3a), , cooeceo, aopaoe pacooee eocapoo eo py.

caoee ooceo peaoo cocooc py 2-e1,3-ocoa 17, 2-e-1,3-ocaoa 13, 2-e-3-oy-1,3ocaoa 15 o poeeo eoo oypex pea.

Opeeeo, o aoc yex eepoo pea c eaoaeao eec py:

O O O S O N i-C4H> > C6HC6HC6Ha o, aea 1,3-ocoae 17 ooo aoo copoa a ao cep po yee peaoo cocooc, a a ao aoa - e ce.

3. Baoece aex 1,3-ocaoaao c aoycyc po Ha pepe pea 2-e-1,3-ocaa 18 c eaoaeao o yeo e ppo aaaopa yco pea a xo coca opayxc poyo (a. 3) O O C6HN2CHCO2CH[Rh] -NCH2Cl2, 20oC CO2CHH(2a) O O CO2CH3 H(2e) 5 O O + C6HC6HH(3a) H(3a) uc-mpac-oyee peya oaa, o pea 2-e-1,3ocaa 18 c eaoaeao pcyc Rh2(CH3CO2)4, po opaoa cec oepx 1,4-oceao c peyece coepae uc-op 19, oa a poeee pea pcyc Cu(CF3SO3)po opoa mpac-oepa 19. p yee eepayp pea o 800C cepeoceeoc yeaec, coepae cepeooepo caoc pepo pa.

Taa Be eepayp ppo aaaopa a coca poyo pea 2-e-1,3-ocaa 18 c eaoaeao (co oo: pe pea 2 aca) Mooe cooCoooee peaeTee- O xo oePaco- a pay- aaaop poyo e pe a : aop :

pa,C 19, % mpac- :

uc- Cu(CF3SO3)2 0,02 : 2 : 1 23 7 : 20 CH2ClRh2(CH3CO2)4 0,05 : 1 : 1,34 20 1 : Cu(CF3SO3)2 0,02 : 2 : 1 41 3 : 40 CH2ClRh2(CH3CO2)4 0,05 : 1 : 1,34 30 1 : 80 C2H4Cl2 Cu(CF3SO3)2 0,02 : 2 : 1 40 3 : B pcyc ax aaaopo, a Rh2(CF3CO2)4, Rh(P(C6H5)3)3Cl, CuCl pea 2-e-1,3-ocaa 18 c eaoaeao poxo c opaoae poyo epe ceox oecax.

oe aecee ooo e 1,3-ocao a ye pea 2-e-4-e-1,3-ocaa 20 2-e-5,5-e-1,3ocaa 21 c eaoaeao.

caoeo, o p 200C pea eaoaeaa c 1,3-ocaa 20, 21 CH2Cl2 pcyc 0,5 o.% Rh2(CH3CO2)4 po opaoa 1,4-oceao 22, 23 c xoa 40 46% cooeceo. Heoxoo oe, o peaoo acce poy epe eocapoapea o C(2)-O(3)-c 1,3-ocaa 20 e oapye. Opaoaec 1,4-ocea 22 peca coo cec yx cepeooepo*, c peyece coepae ( 90%) uc-op.

RR3 4 O N2CHCO2CH1 + RO C6H20, Rh2(OAc)4, -N20oC CH2Cl2, RRR3 3 -RhLn 4 O R3 R1 4 O RO+ C6HO 6 C6HCHCO2CHCH RhLn CO2CHRR Ha CO2CHO O RRO He O R3 C6H5CO2CHC6H+ RHa Ha uc 22, mpac 20, 22: R1 = R2 = H; R3 = CH3;

21, 23: R1 = R2 = CH3; R3 = H epeco, o cyae 1,3-ocaa 21 poyax pea mpacop e oapyeo. Baoece poeae c opaoae uc-oepa 6,6-e-2-eocapo-3-e-1,4-oceaa uc-23 c xoo 46%.

a p apepoa 1,3-ocoao exa opaoa 1,4oceao 19, 22, 23 ae opaoae a oceyy 1,2epepypoy (epepypoa Ceca). B pax a ycox yaay pea yac ocyec oo poox eaea. Ta 1,3-oca, 1,5-ocacpo[5.5]yea, 4-e-, 2,2,4-pe-, 2opo-4-e-1,3-oca pcyc Rh2(CH3CO2)4 e cya pea c eaoaeao peaoo acce pcycy * - yae uc- mpac-oep ee peaoo acc eoo oooo xpoaopa poy peoa eocapoapea eoe p yapoo aeoo co.

Cepeox 1,4-oceao ycaoea a ocoa aaa e xecx co CCB cepax MP 1H 13C oepea c oo eo Oepxayepa.

Ta, cepax MP 1H oepx 5-e-2-eocapo-3-e1,4-oceaao 22 poo eepoa opay cao ecae ccoe cce: yxcoy - (poo H(2) H(3)) c ao ocao CCB 3J2,3 pao 9.2 (mpac-oep) 4.8 (uc-oep) occoy, oopo p pooa, axoec -ooe aoa copoa, peopy p = 3.5-5.0 ... Oecee yeoo caa p 4.65 .. pooy H(3) mpac- 22 o ae oepeo NOE cepeo. p oye aoa H(3) a pooax eoo oa aaec NOE-e, pa 2%, ocycy cyae oye pooa H(2).

Bo o pacooe eoo eoo aecee cea a ocoa yepoo cepa, acaoo pee HH COSY LR ooeo acpoa a CCB 4J3,5 opa 0.5-1 . Hae NOE-ea ey pooa H(3) H(5) (12%) ceecye o x uc-opea.

ooo 1,3-ocaa coeex mpac- uc-22 poo H(6e) H(6a), cepo yaee o oox aoo copoa a p -c, ca e eoex ap aoo copoa, o o pe aopa poo peopye oee co oe, e aca. oea cya ax oca - ooo 15 (3J6a,7a + 3J6e,7e) xapaepye oopa caoo peca ceeoo a.

epeco, o aoece 4-e-1,3-ocaa 24 c o po aoycyco co eco oaeoo poya epe ocapoapea o c O(1)-C(2) po opaoa mpac-oepa ooo pa 5-e-1,3-ocea-4-apooo co mpac-25 c xoo 28 %.

H(5a) O OEt2 1 BFC6H+ N2CHCO2CH2CHO 910 2 -N2 O 4 2 O C6H3 COCH2CHH(4a)O H mpac B cepe MP 13C cxooo coee 24 yepo ao C(2) peopye e pea p 93,7 ... pcyce oo caa yepoo cepe coee mpac-25 yaae a coxpaee cpyypoo paea O-CH2-O-. B cepe MP 13C poya mpac-25 ye ca 77.9 ..

oocc aoy yepoa C(4), caoy c ocapoo pyo, a ye 43.2 .. oycoe yepoo C(5), ca c e aecee. Ha o ae yaae pcyce cepe MP H coee yeoo caa 4.07 .. pooa p aoe C(4), yeoo caa pooa 2.60 .. p aoe C(5). Bea ao CCB aoo H(4) H(5) (3JH(4)H(5) = 7,67 ) e oac 7-12 , o, coaco epayp a, yaae a mpac-opea pooo H(4) H(5), , cooeceo, mpac-pacooee eo ocapoo py. Ha opaoae 1,3-oceaa yaa yee ca oac 3.72-4.00 .. aoa H(7) 1.60-1.90 .. aoa H(6), oope ax cpyyp.

B pcyc aaecoo oeca Cu(CF3SO3)2 p 400C 2-e-1,3-ocea 26 peapye c eaoaeao c opaoae oo mpac-oep eooo pa 3-e-1,4-ocoooa-2apooo co mpac-27 c xoo 23%.

H(3a) Cu(CF3SO3)1 O O + N2CHCO2CH3 O H3CO2C Ph O Ph CH2Cl2, 400C H(2a) mpac- B cepax MP H coee mpac-27 poo eepoa H(2) H(3) opaoa yxcoy ccey c ao CCB J=8.98 , poo H(2) H(3) peopy oac 4.05 .. 4.52 .. cooeceo.

a pooa H(5), axoec -ooe aoy copoa O(4) peopy p 3.80-4.00 ... a pooa H(8), axoec -ooe aoy copoa O(1), peopy oac 4.16-4.27 ... Oecee yeoo caa p 4.52 .. pooy H(3) mpac-oepe o oepeo NOE-cepeo.

Opeeee paepa a a peaoy cocooc py poox eaea 17, 18, 26 poeeo eoo oypex pea. Haeo, o ee aea aee ecex, oope, co oepe, peaoococoee 1,3-oceao.

4. Pea aaoaeaa c ec aea, coepa yoae py B pcyc Rh2(CH3CO2)4 poee pea eaoaeaa c yoaoae 1,3-ocoaa e-(4-ee1,3ocoa)ao 28 2,2-e-4-poce-1,3ocoao 29.

caoeo, o pea coee 28 c eaoaeao pcyc poeoo aaaopa poeae ceo a epee eocapoapea o c N-H, c opaoae eceoo poya - eooo pa N-e-N-(4-ee-1,3-ocoa)aoycyco co 30 c xoo 82%.

CH2NCH2CO2CHCH2NH Rh2(CH3CO2)4 C6HC6H+ N2CHCO2CHO O O O CH2Cl2, 40oC B cepax MP 1H coee 30 pcycye ca 4.23 .., paea pooa eeoo py, axoec p aoe aoa.

Aaoo poeae pea cpa 29 c eaoaeao pcyc Rh2(CH3CO2)4. poyo epe eocapoapea o c C-O eepoa peaoo acce e aaec.

CH2OCH2CO2CHCH2OH Rh2(CH3CO2)+ N2CHCO2CHO O O O CH2Cl2, 400C CH3 CHCH3 CH29 B cepe MP 1H coee 31 pcycy ca 3.62 .., paea pooa eoc-py ca 4.01 .., paea pooa eeoo py. B cepe MP 13C coee 31 ca oac 51.38 .. oycoe pcyce eoc-py, a ca 68.24 .. oec eeoo pye, cao c apo yepo aoo.

Meoo oypex pea a opeeea oocea peaoa cocooc 1,3-ocoao 28 29. Haeo, o epee eocapoapea o c O-H, poeae 2 pa cpee, e o c N-H.

Ha ycaoeo, o, a cyae c poccoepa 1,3-ocoao 29, 5--5-poce-1,3-oca 32 peapye c eaoaeao pcyc epaaeaa po, opay oo poy eepoa - 5--5(2-oc-4-apooc)ec-1,3-oca 34 c xoo 85%.

H5C2 CH2OCH2CO2CHH5C2 CH2OH Rh2(OAc)+ N2CHCO2CHO O O O CH2Cl2, 400C R R R R 34, 32, 32, 34: R=H;

33, 35: R=CHB cepe MP 1H coee 34 pcycye ca 3.68 .., paea pooa eoc-py ca 4.06 .., paea pooa eeoo py, cao c apo yepo aoo. B cepe MP 13C coee 34 ca oac 51.6 .. oepae pcyce eoc-py, ca 71.4 .. oec eeoo pye p apoo yepoo aoe.

poccoepa ea - 2,2-e-5--5-poce-1,3oca 33 pcyc epaaeaa po peapye c eaoaeao opay 2,2-e-5(2-oc-4-apooc)ec-1,3-oca 35 c xoo 75%.

B cepe MP 1H coee 35 pcycye ca 3.62 .. paea pooa eoc-py ca 4.06 .. paea pooa eeoo py. B cepe MP 13C coee 35 ca oac 51.63 .. - oepae pcyce eoc-py, ca 71.39 .. oec eeoo pye.

caoeo, o p ec eocapoapea a opy cec 4-poce-1,3-ocaaa 36 5-poc-1,3-ocaa OH CH2OH CH2OCH2CO2CH3 OCH2CO2CHN2CHCO2CH+ O O O O-N2 O O + O O 37 38 (poy oeca epa c opaeo) pcyc epaaeaa po opayc pax oecax cooecye - ecee p 38 39 (o xo 90 %). Bo pa aoc coee 36 37 acoo a, o ooa o oepo poy pea e yaoc.

oyee peya xopoo coacyc c pee paee oyoax paoax a o o, o aocapoape a opo aee epc o O-H c epx cpo, e o C-O c ecx aeae.

Bo 1. caoeo, o aoece ooo pa aoycyco co c 2-e-2-a-1,3-ocoaa po cooecy o pa 3-e-3-a-1,4-oca-2-apooo co c peyece opaoae cepeooepo, coepax ay pyy aopao ooe.

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