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Ha paax pyoc ETPOB MTP AHATOEB ATATECE PEA ECX AETAE C AOAPOHHM COEHEHM Ceaoc 02.00.03 Opaeca x ABTOPEEPAT ccepa a cocae yo cee aaa xecx ay a - 2002 2 Paoa oea a aepe Oa aaeca x coo ocyapceoo eoo execoo yepcea aopaop eaoopaecoo cea aaa cya opaeco x coo ayoo epa Poccco Aae ay Haye pyooe: oop xecx ay, poeccop oc Cee Coooo, aa xecx ay, cap ay copy, Cyaoa Pa Mapceea Oae ooe: oop xecx ay, pocypa Mapa Baeoa oop xecx ay, eaoa Bepa aoa Beya opaa apc ocyapce ec yepce aa ccepa cococ 26 eap 2002 oa 15 oo aco a acea ccepaooo coea 212.289.01 co ocyapceo eo execo yepcee o apecy: 450062, a, y. ocoao, 1.

C ccepae oo oaoc ayo oee coo ocyapceoo eoo execoo yepcea ayo oee cya opaeco x H PAH Aopeepa paoca op 2002 oa e cepeap ccepaooo coea poeccop A.M. CPH 3 OA XAPATEPCTA PAOT Ayaoc e. ece aea x eepoaao poo pec opaeco cee a peae, oypoy, cxoe eeca p oye ooec ax oeo peapao. Cpe x pea aoe aee e pepae o ece apeo paoo cpoe. Ocoo ceye e pea ecx aeae c aocapoapea, eeppye aoycycx po. eco, o o coco epc o c yepo-copo oaeaoo paea c opaoae ex ooyoax eepoecx coee. ooy yee cpyyp ecx aeae a peo- cepeoceeoc x aaecoo aoec c aoapo coee ec ayao aae.

Paoa oea cooec c aae Mopaoa Pocc o eaecoy ay cceoae aoec eepoo c aoapo coee c e oye aaecx peao peaeo pooo cepa ec a 2001-2005 . paax aa MHT Haye oco eoo oye aooax xecx poyo, eepao eeo popa epa (pa 10-1.5/2000) ceao popa Poccco aae ay o oepe oox yex Pocc (pa 136).

e pao:

- yee aooepoc aoec ecx aeae x eepoaaoo c aoapo coee pcyc cox eaooecx aaaopo;

- opeeee yco pea, oeceax coy peo- cepeoceeoc opaoa poyo.

Haya oa. Bepe yeo e cpyyp aeae eae a peo- cepeoceeoc x aoec c aoapo coee.

caoeo, o xoe pea ceeo opayc poy epe aocapoapea o c O(1)-C(2) ecepx 1,3ocaoaao.

oaao, o ecepe 1,3-ocoa opay 2,3,5paee 1,4-oca c aopa pacooee aecee.

peoe o aaec eo cea aex 1,4oceao, 1,4-ocaao 1,4-ocao y epe eocapoapea, eeppyeoo eaoaeaa, o c C-O C-S pcyc e- pocoepax aaaopo.

paeca eoc pao. oopa yco pea aoycycoo pa c ecep 1,3-ocaoaaa, oeceae coy peo- cepeoceeoc opaoa poyo.

Hae yco ceeoo epe aocapoapea o c yepo-eepoao eepoaaoo ecx aeae.

caoeo e ppo eepoaoa a peoceeoc aoec aocapoapeo c 1,3-ocaeepooeaa Peya pao cooa paax HT Pea papao ayo-execo oyea cea peao.

Papaoa aopaope eo 4-x ox eec cooa aece peao: eooo pa 2-e-1,4-ocaa-3apooo co; eooo pa 3-e-4-oy-1,4-oca-2apooo co; eooo pa 3-e-5-e-1,4-oca-2apooo co; ooo pa 3-e-5-xope-1,4-oca-2apooo co. ae coee e epee aax peao.

Apoa pao. Peya pao ooe ocye a Mooeo ayo oe Opaeca x XX ee (Moca, 2000), XIII XIV Meyapox ayo-execx oepex Xece pea, peae poecc aooao x (Tya, 2000 a, 2001), Mooex ayx oax o opaeco x (Eaepyp, 2000 2002), Meyapoo oepe Modern Problems of Aliphatic Diazo Compounds Chemistry (S.-Petersburg, 2000), I Bcepoccco oepe o x eepoo a A.H.oca (Cya, 2000), 9th Meeting on Stereochemistry (Prague, Czech Republic, 2002), Meyapoo oepe Opaec ce oo coe (C. eepyp, 2002).

ya. o ee ccepa oyoa 5 ayx cae, eco oao a oepex.

Cpyypa o ccepa. ccepaoa paoa oea a 102 cpaax aocoo eca ae oop epayp, ocyee peyao, cepeay ac, o, cco epayp (112 aeoa), 3 a 5 pcyo.

OCHOBHOE COEPAHE PAOT 1. aaece pea ex eepoo c aaoaeaa M y aoece oaex 1,3-ocoao 1-4* c aaoaeaa. B peyae pea oye 1,4-oca 5-8 - poy epe aocapoapea o C(2)-O(1) c (a. 1). p o ooe poy epe aocapoapea o c C(2)-O(3) peaoo acce e oapye.

* - 1,3-ocoa 1 3 peca coo cec uc-, mpac-oepo (coooee 45 : 55) CH2X CH2X 6 a O O 1 + O O N2CHCO2R-NRR3O2C R1 RH R1-4 5-1, 5: R1=H, R2=C6H5, R3=CH3, X=H;

2, 6: R1=R2=R3=CH3, X=H;

3, 7: R1=H, R2=C6H5, R3=C2H5, X=Cl;

4, 8: R1=R2=CH3, R3=C2H5, X=Cl Taa Be ppo aaaopa a xo poyo pea aoycycoo pa c ecep 1,3-ocoaa 1-(co oo: pe pea 3 aca) Mooe Tee- coooee poy aaaop paypa, R1 R2 R3 X peaeo pea C a : ao- (xo, %) p : (1-4) H C6H5 CH3 H 5 (99) CH3 CH3 CH3 H 6 (40) BF3O(C2H5)2 95 0,05 : 1 :H C6H5 C2H5 Cl 7 (55) CH3 CH3 C2H5 Cl 8 (17) H C6H5 CH3 H 5 (91) CH3 CH3 CH3 H 6 (56) Cu(CF3SO3)2 95 0, 01 : 1 : H C6H5 C2H5 Cl 7 (70) CH3 CH3 C2H5 Cl 8 (20) H C6H5 CH3 H 5 (61) CH3 CH3 CH3 H 6 (8) Rh2(CH3CO2)4 40 0,01 : 1 :1,H C6H5 C2H5 Cl 7 (15) CH3 CH3 C2H5 Cl 8 (<1) caoeo, o xo poyo aoec aaoaeaa c ae 1,3-ocoaa 1-4 opeeec ppoo epaoo aoa aaaopa. To a, o aoece aoycycoo pa ye poeae c poo eaea 1 3, xopoo coacyec c exao 1,2-aoo epepypo. B cooec c exao p pya pya epexoo coco pecae coo coo paa, ae aecee, capyx eo aoap cope, cococye poea poecca. o o e pe eee aoa xopa e ce peaoo cocooc 1,3-ocoao, , a cece, yee xoa cooecyx 1,4-ocao.

Cpyypa pocpaceoe cpoee eex coee 5-1 ycaoe a ocoa ax cepo MP H C c peee NOE-cepea.

B cepe MP C coee mpac-5 ae cao oac 65-80 .., paeax aoa yepoa, axoc -ooe aoa copoa, o 1,4-ocaooo paea.

H(2a) H(6a) 10 7 H(6e) O H3CO2C O Ph CHH(3a) H(5a) mpac B cepe MP H 1,4-ocaa mpac-5 yee ca 4.04 .. 4.68 .., a ceye epaypx ax, oocc pooa p yepox aoax C(2) C(3), cax c eocapoo eo pya cooeceo. p ace yea 4.04 .., paeaeo pooy H(2a), aaec N OE - e (=4%) a acao pooe H(6a), o oaae acaoe pacooee pooa H(2a). Bea ao CCB 3JH(2a)H(3a) = 9,1 ae yaae a acay opea pooo H(2a) H(3a) , cooeceo, aopaoe pacooee eocapoo eo py ( epaypx ax eco, o mpac-pacooe pooa cooecye aa CCB eaa oac 7-12 , a uc-pacooe oac 2-6 ).

Acay opea pooa H(5a) oepa e ax CCB: 3JH(5a)H(6a) =10,15, 3JH(5a)H(6e) = 2,64 .

B cepe MP H coee mpac-6 pcycye ye ca 3.97 .., oece acaoy pooy H(5a), p oye oopoo aaec e Oepxayepa (=3,3%) a acao eo pye, p aoe C(3) (ce 1.23 ..).

H(2a) H(6a) H(6e) O H3CO2C O H3C CHCH3 H(5a) mpac oaaeco acao opea pooa H(5a) ec ae yx ax CCB: 3JH(5a)H(6a) = 11,2 3JH(5a)H(6e)= 2,86 . Ceoaeo, ea pya p aoe C(5) opepoaa aopao. Bea po yepo-pooo CCB 1JC(2)H(2a) = 146, 4 (p acao opea pooa H(2), coee mpac-5, pa yepo-pooa CCB JC(2)H(2a) = 147,6 ) ceecye o acao opea pooa H(2a) , ceoaeo, aopao pacooe eocapoo py.

B cepe MP H coee mpac-7 yee ca 4.03 .. 4.68 .., a ceye epaypx ax, oocc pooa p yepox aoax C(2) C(3), cax c ocapoo eo pya cooeceo.

H(2a) 10 O H3CH2CO2C O Ph CH2Cl H(3a) H(5a) mpac Bea ao CCB 3JH(2a)H(3a) = 9,11 , oaae acay opea pooo , ceoaeo, aopaoe pacooee ocapoo eo py. Acay opea pooa H(5a) oepa e ax CCB: JH(5a)H(6a) =9.9 , JH(5a)H(6e) = 2,60 .

1 B cepe MP H coee mpac-8 e CCB : JH(6e)H(6a) = -11.38 , 3JH(5a)H(6a) = 11.4 oepa acay opea pooa H(5a) , a cece, aopaoe ooee xopeo py.

H(2a) 11 10 O H3CH2CO2C O CH2Cl H3C CH3 H(5a) mpac B yepo cepe, co pee COLOC, aaec pocc- ey yepo aoo C(5) (69,1 ..) pooa p yepoo aoe C(15) (26,3 ..), o oaae epee ocapoeea o c O(1)-C(2) cxooo 1,3-ocoaa 4.

Baoece 2-e-2--1,3-ocoaa 9 2-e-2-y-1,3ocoaa 10 c aoeao yac poec oo cx ycox e cycpaa, p eepaype 110-1150C pcyc BF3O(C2H5)c xoo 1,4-ocao 11, 12 34% 29% cooeceo, o ae ec oepee capye po eoo aece o 2-o ooe 1,3-ocoaa epexoo coco. oyee coe p 11, 12 peca coo cec cepeooepo c peyece (oee 80%) coepae mpac-oepa.

BF3 OEt2 6 N2CHCO2C2H5 + O O O O 2 110-115oC R CHCHH3CO2C H R 9, 10 11, 9, 11: R=C2H5;

10, 12: R=C4H1 B cepax MP H C eeoo coee mpac-11 ea po yepo-pooo CCB 1JC(2)H(2a) = 145,9 ceecye o acao opea pooa H(2a) aopao pacooe ocapoo py.

H(2a) 9 H3CH2CO2C O O H3CH2C 14 CHmpac B cepax NOESY aaec pocc- ey pooa (1.2 ..) paea eeoo pye p aoe C(3) pooo H(2) (3.5 ..), o yaae a x uc-opea, cooeceo, ocapoa a py opepoa aopao, o ec e mpac-pacooee.

B cepe MP 13C e xecx co cao C(2), C(3), C(12) aoo, pae 80.7, 73.7, 16.9 .., oo xec ca cao aaox aoo coee mpac-11 (79.9, 72.7, 15.7 ..) oepa acay opea eo py p aoe C(3) aopay opea ocapoo py p aoe C(2) , ceoaeo, mpac-pacooee ocapoo yo py mpac-12.

H(2a) 10 9 H3CH2CO2C O 3 O H3CH2CH2CH2C 16 15 14 CHmpac Ta opao, a oaao, o aaoaea aoecy c ae 1,3-ocoaa pcyc Rh2(CH3CO2)4, Cu(CF3SO3)2 c opaoae cooecyx 1,4-ocao. Pea poeae ceeo o c C(2)-O(1) eepoa, c peyece opaoae mpacoepa.

Meoo oypex pea o oaao, o yee a aea oo pacoo o coe peaoo cocooc cey p:

CHCH2Cl CH> > > O O O O O O CH3 CHC6HC6HCH2Cl > > > O O O O O O CH3 C2HCH3 C4HCH3 CH2. Pea eaoaeaa c 1-oca-3-o- 1-oca-3-aaoeaa 13, Haeo, o 2-e-1,3-ocaoa 13 peapye c eaoaeao pcyc Rh2(CH3CO2)4, opay 2,3-ae 1,4-ocaa 14 e cec uc- mpac-oepo.

C6HC6HO [Rh] O S +N2CHCO2CHS CHCO2CHCH2Cl2, 400C [Rh]L 13 72% H(2a) H(2a) C6H2 O C6H+ O 5 S H(3e) S CO2CHCO2CHH(3a) uc mpac 3 : Ocyce peaoo acce poyo epe eocapoapea o c C-O ocec e, o poeyoo opayec S- aeo ycoee O-o.

eee eepayp oaae cyeceoe e a o xo mpac- uc-1,4-ocaao 14 (a.2).

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