Photochemical type II reaction of atropchiral benzoylformamides to point chiral oxazolidin-4-ones. Axial chiral memory leading to enantiomeric resolution of photoproducts

被引:82
作者
Jesuraj, Josepha L. [1 ]
Sivaguru, J. [1 ]
机构
[1] N Dakota State Univ, Dept Chem & Mol Biol, Fargo, ND 58105 USA
基金
美国国家科学基金会;
关键词
ALPHA-OXOAMIDES; AMIDES; PHOTOCYCLIZATION; AUXILIARY; LACTAM;
D O I
10.1039/c0cc00470g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Atropisomeric benzoylformamides 1 undergo Type II reaction leading to cis-2 and trans-2 oxazolidin-4-one photoproducts. The N-C(Aryl) chiral axis is maintained during the course of the phototransformation in spite the reaction proceeding through a near planar intermediate(s). As the rotational barrier of the N-C(Aryl) chiral axis in the cis-2 and trans-2 photoproducts is lowered when compared with the reactant 1, the isolated optically pure trans-2 isomer is converted to the ent-cis-2 isomer without affecting the C-5 stereogenic center, resulting in resolution of the cis-2 enantiomers.
引用
收藏
页码:4791 / 4793
页数:3
相关论文
共 25 条
[1]   PHOTOCHEMICAL-REACTIONS OF ALPHA-OXO AMIDES - NORRISH TYPE-II REACTIONS VIA ZWITTERIONIC INTERMEDIATES [J].
AOYAMA, H ;
SAKAMOTO, M ;
KUWABARA, K ;
YOSHIDA, K ;
OMOTE, Y .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (07) :1958-1964
[2]   Enantiospecific Photochemical Norrish/Yang Type II Reaction of Nonbiaryl Atropchiral α-Oxoamides in Solution-Axial to Point Chirality Transfer [J].
Ayitou, Anoklase Jean-Luc ;
Jesuraj, Josepha L. ;
Barooah, Nilotpal ;
Ugrinov, Angel ;
Sivaguru, J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (32) :11314-+
[3]   Light-Induced Transfer of Molecular Chirality in Solution: Enantiospecific Photocyclization of Molecularly Chiral Acrylanilides [J].
Ayitou, Anoklase Jean-Luc ;
Sivaguru, J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (14) :5036-+
[4]   PHOTOCYCLIZATION OF ALPHA-KETO AMIDES IN HOMOGENEOUS SOLUTION AND AQUEOUS CYCLODEXTRIN MEDIA - THE ROLE OF ZWITTERIONS AND DIRADICALS IN PHOTOINDUCED ELECTRON-TRANSFER REACTIONS [J].
CHESTA, CA ;
WHITTEN, DG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (06) :2188-2197
[5]   Atropisomers and near-atropisomers: achieving stereoselectivity by exploiting the conformational preferences of aromatic amides [J].
Clayden, J .
CHEMICAL COMMUNICATIONS, 2004, (02) :127-135
[6]   Rotational features of carbon-nitrogen bonds in axially chiral o-tert-butyl anilides and related molecules.: Potential substrates for the 'prochiral auxiliary' approach to asymmetric synthesis [J].
Curran, DP ;
Hale, GR ;
Geib, SJ ;
Balog, A ;
Cass, QB ;
Degani, ALG ;
Hernandes, MZ ;
Freitas, LCG .
TETRAHEDRON-ASYMMETRY, 1997, 8 (23) :3955-3975
[7]   ATROPOSELECTIVE THERMAL-REACTIONS OF AXIALLY TWISTED AMIDES AND IMIDES [J].
CURRAN, DP ;
QI, HY ;
GEIB, SJ ;
DEMELLO, NC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (07) :3131-3132
[8]  
Giese B, 1999, ANGEW CHEM INT EDIT, V38, P2586, DOI 10.1002/(SICI)1521-3773(19990903)38:17<2586::AID-ANIE2586>3.0.CO
[9]  
2-K
[10]  
Griesbeck AG, 2001, ANGEW CHEM INT EDIT, V40, P577, DOI 10.1002/1521-3773(20010202)40:3<577::AID-ANIE577>3.0.CO