Zirconium-Promoted Ring Opening. Scope and Limitations
详细信息 查看全文
- 作者：Nathalie Cé ; nac ; Maria Zablocka ; Alain Igau ; Gé ; rard Commenges ; Jean-Pierre Majoral ; and Aleksandra Skowronska
- 刊名：Organometallics
- 出版年：1996
- 出版时间：February 20, 1996
- 年：1996
- 卷：15
- 期：4
- 页码：1208 - 1217
- 全文大小：406K
- 年卷期：v.15,no.4(February 20, 1996)
- ISSN：1520-6041
文摘
Hydrozirconation by means of[Cp2ZrHCl]n (2) ofphospholenePhPCH2CH=CHCH2(1)leads to the 
-zirconated phospholane 3 which reacts withphosphenium saltsR2P+OSO2CF3-(4, R = NiPr2;5, R = NCy2) to give unsaturated acyclic1,1-diphosphines 6 or 7.Compound3 also reacts with other electrophiles like[CH2=NMe2]Cl,tBuCOCl, orHOSO2CF3 leadingto unsaturated phosphinesPhP(R)(CH2)2CH=CH2,8 (R = CH2NMe2), 9(R = C(O)tBu), or10 (R = H), respectively. Hydrozirconation of2,5-dihydrofuran (12) or 2,3-dihydrofuran(13) affords the acyclic zirconated speciesCp2Zr(Cl)O(CH2)2CH=CH2(15), which reacts with4, Ph2PCl,[CH2=NMe2]Cl, PhCOCl, orHOSO2CF3 to give, via exchange reactions,thecorresponding substituted olefines 16-20. Treatmentof 12 or 13 with 2 equiv of 2 leadstodizirconated compoundCp2Zr(Cl)O(CH2)4Zr(Cl)Cp2(21) which reacts with Ph2PCl (2equiv)to give the phosphino-phosphinitePh2PO(CH2)4PPh2(22) isolated as its disulfide 23.2-Methyl-4,5-dihydrofuran (24) treated first with 2equiv of 2 and then with 2 equiv ofPh2PCl affords the phosphino-phosphinitePh2PO(CH2)5PPh2(26). Hydrozirconation of 2,5-dimethoxy-2,5-dihydrofuran (28) with 2 equiv of 2gives rise to Cp2Zr(OMe)Cl (31)andCp2Zr(Cl)O(CH2)2CH=CHOMe(33), which react further with Ph2PCl (2equiv) leading tophosphinites Ph2POMe (34) andPh2PO(CH2)2CH=CHOMe(35). Addition of 2 to 1-benzyl-3-pyrroline (36) allows the formation of the -zirconatednitrogen five-membered ringPhCH2N(CH2)2CH(ZrCp2Cl)CH2(37). 37 reacts with Ph2PClgiving rise to the acyclicaminophosphinePh2PN(CH2Ph)(CH2)2CH=CH2(38) and to a substitute pyrroline39.Derivative 37 also reacts with 4 to give thesaturated nitrogen heterocycle 42, while itreactswith PhCOCl or HOSO2CF3 to afford thecorresponding linear speciesPhC(O)N(CH2Ph)(CH2)2CH=CH2 (44)or the amineHN(CH2Ph)(CH2)2CH=CH2(45). Hydrozirconation of 38followed by addition of Ph2PCl and then addition ofS8 gives the aminophosphine-phosphinedisulfidePh2P(S)N(CH2Ph)(CH2)4P(S)Ph2(46). Hydrozirconation of oxygensix-memberedrings such as 3,4-dihydro-2H-pyran (53) and2-methoxy-3,4-dihydro-2H-pyran (55)isdiscussed as well as the hydrozirconation of a seven-membered ring,cis-dihydro-1,3-dioxepin(62). The behavior of 3-sila- (47) or3-boracyclopentene (48) is also presented.
-zirconated phospholane 3 which reacts withphosphenium saltsR2P+OSO2CF3-(4, R = NiPr2;5, R = NCy2) to give unsaturated acyclic1,1-diphosphines 6 or 7.Compound3 also reacts with other electrophiles like[CH2=NMe2]Cl,tBuCOCl, orHOSO2CF3 leadingto unsaturated phosphinesPhP(R)(CH2)2CH=CH2,8 (R = CH2NMe2), 9(R = C(O)tBu), or10 (R = H), respectively. Hydrozirconation of2,5-dihydrofuran (12) or 2,3-dihydrofuran(13) affords the acyclic zirconated speciesCp2Zr(Cl)O(CH2)2CH=CH2(15), which reacts with4, Ph2PCl,[CH2=NMe2]Cl, PhCOCl, orHOSO2CF3 to give, via exchange reactions,thecorresponding substituted olefines 16-20. Treatmentof 12 or 13 with 2 equiv of 2 leadstodizirconated compoundCp2Zr(Cl)O(CH2)4Zr(Cl)Cp2(21) which reacts with Ph2PCl (2equiv)to give the phosphino-phosphinitePh2PO(CH2)4PPh2(22) isolated as its disulfide 23.2-Methyl-4,5-dihydrofuran (24) treated first with 2equiv of 2 and then with 2 equiv ofPh2PCl affords the phosphino-phosphinitePh2PO(CH2)5PPh2(26). Hydrozirconation of 2,5-dimethoxy-2,5-dihydrofuran (28) with 2 equiv of 2gives rise to Cp2Zr(OMe)Cl (31)andCp2Zr(Cl)O(CH2)2CH=CHOMe(33), which react further with Ph2PCl (2equiv) leading tophosphinites Ph2POMe (34) andPh2PO(CH2)2CH=CHOMe(35). Addition of 2 to 1-benzyl-3-pyrroline (36) allows the formation of the -zirconatednitrogen five-membered ringPhCH2N(CH2)2CH(ZrCp2Cl)CH2(37). 37 reacts with Ph2PClgiving rise to the acyclicaminophosphinePh2PN(CH2Ph)(CH2)2CH=CH2(38) and to a substitute pyrroline39.Derivative 37 also reacts with 4 to give thesaturated nitrogen heterocycle 42, while itreactswith PhCOCl or HOSO2CF3 to afford thecorresponding linear speciesPhC(O)N(CH2Ph)(CH2)2CH=CH2 (44)or the amineHN(CH2Ph)(CH2)2CH=CH2(45). Hydrozirconation of 38followed by addition of Ph2PCl and then addition ofS8 gives the aminophosphine-phosphinedisulfidePh2P(S)N(CH2Ph)(CH2)4P(S)Ph2(46). Hydrozirconation of oxygensix-memberedrings such as 3,4-dihydro-2H-pyran (53) and2-methoxy-3,4-dihydro-2H-pyran (55)isdiscussed as well as the hydrozirconation of a seven-membered ring,cis-dihydro-1,3-dioxepin(62). The behavior of 3-sila- (47) or3-boracyclopentene (48) is also presented.