Enantioselective Diethylzinc Addition to N-(Diphenylphosphinoyl)imines Catalyzed by Binaphthyl-based N,O-Ligands
- 발행기관 고려대학교 대학원
- 발행년도 2004
- 학위명 박사
- 학과 대학원:화학과
- 식별자(기타) DL:000014914171
- 서지제어번호 000045213442
초록/요약
The addition of organozinc to N-(diphenylphosphinoyl)imines is a conven-ient method for the preparation of optically enriched amines. However, only a few examples of enantioselective alkylation of imine functionality have been reported. In this study, new binaphthyl-based N,O-ligands and their thiophosphor-amide derivatives ligands were prepared from optically pure binaphthol and applied them to the enantioselective addition of diethylzinc to N-(diphenyl-phosphinoyl)imines. In the case of 2-dialkylaminomethyl-2’-hydroxy-1,1’-binaphthyl ligands, en-antiomeric excess of up to 92% could be obtained using a stoichiometric amount of the ligand. When 2-(dialkoxyphosphinoyl)aminomethyl-2’-hydroxy-1,1’-binaphthyl liga-nds were used as a catalytic chiral ligand in Cu(OTf)2-promoted catalytic asymmetric addition of diethylzinc to N-(diphenylphosphinoyl)imines, an enantiomeric excess of up to 85% could be realized.
more목차
I. 서론……………………………………………………1
II. 결과 및 고찰…………………………………………9
1.리간드의 합성………………………………………9
2.N,O-리간드를 이용한 다이에틸아연 첨가반응…16
3.싸이오포스포아마이드 리간드–구리 착물을 이용한
아연 첨가반응………………………………………20
III. 결론…………………………………………………25
IV. 실험…………………………………………………26
1.기기 및 시약…………………………………………26
2.리간드 합성…………………………………………27
3.N-다이페닐포스핀오일이민의 합성………………50
4.다이에틸아연 첨가반응……………………………51
V. 부록…………………………………………………54
VI. 참고문헌……………………………………………57
