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Ha paax pyoc HEOBA HATA EHHAEBHA CHTE APHOB OPOAHOB C AOCOHATHM CTPTPHM PAMEHTOM Ceaoc 02.00.03 Opaeca x ABTOPEEPAT ccepa a cocae yeo cee aaa xecx ay a - 2002 2 Paoa oea co ocyapceo eo execo yepcee.

HAH POBOTE oop xecx ay, poeccop oc Cee Coooo.

OAHE OOHEHT: oop xecx ay, poeccop op Bap Bopo;

oop xecx ay pocypa Mapa Baeoa.

BEEE PEPTE apc ocyapce yepce.

aa cococ 26 eap 2002 . 1200 aco a acea ccepaooo coea 212.289.01 p co ocyapceo eo execo yepcee o apecy: 450062, . a, y.

ocoao, 1.

C ccepae oo oaoc oee coo ocyapceoo eoo execoo yepcea.

Aopeepa paoca op 2002 .

e cepeap ccepaooo coea A.M. Cp 3 OA XAPATEPCTA PAOT Ayaoc pao. B ocee o eco paaec x ax o, acoc apo opoao. o cao c x o eopeec pa aee, acoc c cooae x coee x poox cee ooec ax eec, xecx cpec a pace p. ae epec a ap opoa, coepae aocoa pae, ocoy cpe x oapye cooee epcee eapcee peapa.

O aoee pocx yox eoo oye aeex apo opoao ec pcoeee cooecyx apeo o o yepo-ao yepoyepo c. B o c pecaec a aya y aaecoe aoece aoocoao c a epee coee. Tae oeoe ae peae oyee opoao, coepax aocoa pae cooecyx -oce.

Ceoaeo, papaoa ycoepecoae eoo oye apo opoao, coepax aocoae aece, ec ayao ooc oeae aaa copeeoo opaecoo cea.

ccepaoa paoa oea cooec c aae Mopaoa P o eaecoy ay HP HT 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.

e pao.

- Papaoa eoo oye apo opoao, coepax aocoay pyy, yee x cpoe pepae.

- Opeeee aopo, x a peo- cepeoceeoc aaecoo pcoee aoaocoao o o yepo-ao yepo-yepo c.

- coepecoae cxe oye opoocoao ooo pa eocopo co.

Haya oa. Bepe papaoa aaec eo cepeoceeoo pcoee aoaocoaa apoaec a paoo cpoe. Opeee yco, oeceae opaoae yax uc-oepo. caoeo e aecee apoaeco pe o a peya pcoee.

Bepe oaao, o p aoec aoocoaa c ypao apaeo poeae opoapoae oo c pacpe a c opaoae eo pao oypae.

poeocppoaa ceeca eoc oye mpac-aeeoo opoaa oepae cooecye oc.

paeca eoc pao. Papaoa ooca peocee eo oye uc-apo peyae aaecoo pcoee opoooo pa aoeocopo co apoaec a.

Ocyece pexca ce mpac-aeex opoao, coepax aocoa pae paec ocyoo ooo pa eocopo co.

ya. o ee ccepa oyoao 2 ca ec 2 oao.

Cpyypa oe pao. ccepaoa paoa coco ee, oopa epayp, ocye peyao, cepeao ac, oo, cca epayp; coep 6 a, 12 cxe, pcyo, cco pyeo epayp ae 109 coo.

OCHOBHOE COEPAHE PAOT 1. Baoece opoooo pa aoeocopo co c a c opaoae ap-2-ocoao.

Ap, coepae aocoay pyy, ocee o pea ae cceoaee, ocoy peca epec ae cea ooec ax eec eapcex peapao.

ece p pax eoo oye apo cpe x aoee poc (cxea 1) c aoece apeo c a (eo a) peo c aea (eo ).

b a N :N + :C + N Cxea oye aocoax poox* cooa aaecoe aoece cooecyeo aocoee c a (eo 1a).

* Bpaa yoy aoapoc poeccopy Roberto Pellicciari copya cya x exoo eapc (yepce . epya, a) a ayo-eoecy oo, oepy ae.

cxo oceaa 1, epe poeyoe coee 2-5 oy eeo opoo p aoeocopo co 6 o eoe Ceepca (cxea 2) c xopo xoo (73%).

O O 48% HBr NCH2OH NCH2Br H2SOO O P(OiPr)O O NCH2P(OiPr) O 95% N2HO O NH AcO-NH3+CH2P(OiPr)2 + NH O NaNO2, AcOH, K2CO3, H2O O N2CHP(OiPr)Cxea ae a epe o yeo oyee ap-2ocoao aaec aoece aopeaea 6 c eeeao 7 (cxea 3).

Ph Ph O Ph H H H N N N Ph (iPrO)P CHN+ + Ph H P(OiPr)Ph P(OiPr)O O O Ph NH-CH=C(Ph)P(OiPr) Cxea M a, o popoecyoa pa eao Zn(II), In(III), Cu(II), Yb(III) eo aapy y pea oecea xopo xo opoooo pa (1,3-eap-2-)ocopo co e cec 8 (uc-) 9 (mpac-) oepo (cxea 3). oo poyo pea ec opoo p (1-e-2-eao)ocopo co 10 (cec uc- mpac-oepo).

y cyap xo apo (8 9) - 65% 54% ocy (a. 1) p cooa aece aaaopo cooeceo Zn(OTf)2 In(OTf)3. p o a cepeoceeoc pcoee cyeceoe e oaae coyeoo aaaopa. Bcoy cepeoceeoc po ae co ca, a Yb(OTf)3 (coooee 8:9 cocae 9:1) In(OTf)(coooee 8:9 cocae >10:1).

Taa Be ppo aaaopa a coca poyo pea aocoee 6 c o 7.

(co oo: coooee a.:6:7=0.1:1.5:1, pacope - CH2Cl2).

aaaop Tee- Bpe O xo Coooee Bxo paypa, pea, poyo o C 8+9, 8:9 % % 25 3 65 1:1 Zn(OTf)2 25 18 63 1:1 0 3.5 51 2:1 25 3 39 9:1 In(OTf)3 25 18 54 4:1 0 3 40 >10:Cu(OTf)2 0 2.5 19 >10: 0 5 37 9:Yb(OTf)25 2 43 9: oyex peyao (a. 1) ceye, o cepeoce- eoc poecca ae ac o yco pea. p 0oC (aaaop In(OTf)3) uc-oep 8 oye c xopo xoo (40%) coo cepeoceeoc. B pcyc Cu(OTf)oeaec coa cepeoceeoc, o xo (19%) uc- oepa 8.

Tae peya epaype ae oo peoo, o pea, aapyea Cu(OTf)2, poeae o ceyey exay (cxea 4).

O PO3iPrR-N+ N2CHP(OiPr)LA LA H RN RPO3iPrRRLAH N R1 N + R2iPrO3P RRCxea Ha epo ca pocxo opaoae eayepoo c, c oopee oeee oey N2. poeyo eaoooppoa ape oepaec yeoo aae co copo cooo ap epoo aoa aoa a. Boa ae ypoeypo yec eeo ap.

ax co ca, a In(OTf)3, Zn(OTf)2, Yb(OTf)3, ooy, peayec o exa pcoee (cxea 5).

RRN: LA N + LA RRRRN: LA N: LA H H + N2 + NRRPO3iPrPO3iPr-NRN R2 PO3iPrCxea Ha epo ca pocxo opaoae oeca eaa c aoo aoa a. Cey ao ec yeoa aaa o aoy yepoa oo yepo-aoo c. aee pocxo eee oey N2 c oopee opaoae apooo a.

oo opoo p (1-e-2-eao) ocopo co 10 opayec c xoo (3%) pcyc Cu(OTf)2, oao cyae aaaopo In(OTf)3, Zn(OTf)2, Yb(OTf)3 eo xo opacae o 10-13% (a. 1). Bepoo, pa aece R1 poeyoo oece oyppye c eo ae (cxea 6), o oepae caaoe peooee o exaax pea.

N RR+ O N2CHP(OiPr)LA LA RO N RP(OiP r2) H +N -N RRRRN N O O RP(OiP r)H P(OiP r)O H P(OiP r)R2 N H RCxea :

Ha o paccopeo e aecee e a xo cepeoceeoc opaoa apo (cxea 7).

R2 RO Ar1 N H CH2Cl2 H N H N R+ + (iPrO)P Ar1 CHNAr1 P(OiPr)2 H P(OiPr)7, 11-O O 8, 19-9, 27-11, 19: Ar1=Ph, R2= p-MeOPh 12, 20: Ar1=Ph, R2= p-CF3Bn 13, 21, 27: Ar1=Ph, R2=CH(Ph)14, 22, 28: Ar1= p-MePh, R2=CH(Ph)15, 23, 29: Ar1= p-ClPh, R2=CH(Ph)16, 24, 30: Ar1= p-CF3Ph, R2=CH(Ph)17, 25, 31: Ar1= p-NO2Ph, R2=CH(Ph)18, 26, 32: Ar1= p-AcOPh, R2=CH(Ph)Cxea Oaaoc, o cepeoceeoc pea ac o ppo aece p aoe aoa e (a. 2). 11 12, oyee apoaecx aeo, peapy c ocoeee 6, opay cooecye poy 19, 20 c ocaoo xopo xoa (4042%) coo cepeoceeoc (coooee uc- (19, 20):mpac- oepo cocae >10:1). Oe, o cyae a 13, coepaeo CH(Ph)2-pyy, cepeoceeoc aae coooee uc- mpacop 21 27 cocae 3:1.

Taa Coca poyo pea aocoee 6 c a paoo cpoe 11-18.

(co oo: coooee a.:6:11-18=0.1:1.5:10oC, pacope - CH2Cl2, aaaop - In(OTf)3).

Ar1 R2 Bpe poy pea Coooee pea, (xo %) oepo uc:mpac Ph Ph 3 8 (40) >10:Ph p-MeOPh 6 19 (42) >10:Ph p-CF3Bn 48 20 (40) >10:Ph CH(Ph)2 6 21 (58) 27 (19) 3:p-MePh CH(Ph)2 24 22 (69) 28 (13) 5:p-ClPh CH(Ph)2 3 23 (75) 29 (9) 8:p-CF3Ph CH(Ph)2 2.5 24 (45) 30 (20) 2:p-NO2Ph CH(Ph)2 2.5 25 (53) 31 (27) 2:p-AcOPh CH(Ph)2 5 26 (69) 32 (17) 4:p aoec aocoee 6 c a 14-18, coepa pae aece apoaeco pe cyape xo cooecyx apo 21-32 yeac o 80-90%.

p o epoo-aeope p-NO2- p-CF3-aece apoaeco pe peo ca cepeoceeoc (coooee uc-:mpac-oepo 24:30 25:31 cocae 2:1). ocaoo coa cepeoceeoc (coooee 26 (uc):32 (mpac) cocae 8:1) a ocya pea c o 15, coepa xop apaooe pa.

o yeo e pax poox In(III) a xo cepeoceeoc pea. oyex ax (a. 3) ceye, o co In(Cl)3 aaecoo e oaae, a po In(Br)oae cepeoceeoc (coooee 21:27 cocae 5:1), o cpae c In(OTf)3 (coooee oepo 21:27 cocae 3:1). Oao cyap xo apo (21+27) pcyc In(OTf)3 pepo 4 paa e, e p aae co In(Br)3. ae, o aaaopa In(Br)3 eoxoa oaa eepaypa pooeoc 15 aco, oa a o ece In(OTf)3 pea paec aaaec a aco p 0oC.

Taa Be poox In(III) a coca poyo pea ocoee 6 c o 13.

(co oo: coooee a.:6:13=0.1:1.5:1, pacope CH2Cl2).

Ar1 R2 aa- Bpe Tee- poy Cooo- aop pea, paypa pea ee o C (xo %) oepo uc:mpac In(OTf)3 6 0 21 (58) 27 (19) 3: 3 0 - - - Ph CH(Ph)2 In(Br) 15 23 21 (16) 27 (3) 5: 3 0 - - - In(Cl) 48 23 ce - Tae oeaoc ece aoee eoo aaaopa In(OTf)3 pax pacopex (a. 4). aea CH2Cl2 a oee op T paec e ea peya pea, oa a oyoe aaec aca cyap xo poyo apepoa (xo oepo 21+27 cocae 82%). p o aea eoo aece ( 7) a ee ( 13) po peoy ce cepeoceeoc.

Taa Be ppo pacope a coca poyo pea aocoee 6 c a 7, 13.

(co oo: coooee a.:6:13=0.1:1.5:1, aaaop - In(OTf)3).

Ar1 R2 Paco- Bpe Tee- poy Cooo- pe pea, paypa, pea ee C (xo %) oepo uc:mpac CH2Cl2 3 0 8 (40) >10:Ph Ph T 1.5 0 8 (36) >10: T 6 -70 8 (38) >10: CH2Cl2 6 0 21 (58) 27 (19) 3:2:Ph CH(Ph)2 T 24 0 21 (39) 27 (21) 3:Toyo 7.5 0 21 (60) 27 (22) Ha a cceoaa pea pacp apooo oa eoo pe uc-4[1-ep-3-(opoococop) ap-2-]ycyco co 26. ppoae coeee 26 eaoe p 23-25oC pcyc aaaopa (10% Pd a ye) poeae c cee papo c yepo-ao co copo apoaecoo pa opaoae epo ao-py (cxea 8). B peyae oye e p 4-[2-ao-2 (opoococop)]ycyco co 33 c xopo xoo (79%).

O Ph Ph P(OiPr)N Pd/C H H HNHP(OiPr)AcO O AcO 6N HCl 90oC O P(OH)NH2*HCl HO Cxea po aa 33 o poxop[1-ao-2-(4-poce)1-]ocopo co 34 ocyec 6N oo pacope coo co p eepaype 90oC eee 28 aco. B peyae eeo poxop 34 oye ee c 87%- xoo.

2.2. Baoece ypaa c opoo po aoeocopo co.

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