Chiral Crown Conformation of Rh2(S-PTTL)4: Enantioselective Cyclopropa nation with α-Alkyl-α-diazoesters

被引:155
作者
DeAngelis, Andrew [1 ]
Dmitrenko, Olga [1 ]
Yap, Glenn P. A. [1 ]
Fox, Joseph M. [1 ]
机构
[1] Univ Delaware, Dept Chem & Biochem, Brown Labs, Newark, DE 19716 USA
关键词
C-H INSERTION; BETA-KETO-ESTERS; DIRHODIUM(II) CARBOXYLATES; CARBONYL YLIDES; CYCLOADDITION REACTIONS; RH(II) CATALYST; CONSTRUCTION; ADAMANTYLGLYCINE; SELECTIVITY;
D O I
10.1021/ja9026852
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Herein, we provide crystallographic and computational evidence that Hashimoto's Rh-2(S-PTTL)(4) catalyst adopts a "chiral crown" conformation with a reactive chiral face and an unreactive achiral face. In Rh-2(S-PTTL)(4), all four tert-butyl groups are aligned on the same face of the catalyst, and each C-(t-Bu) bond is roughly parallel. to the central Rh-Rh bond. This orients the four phthalimido groups on the opposite face of the catalyst. Also described is an enantioselective and diastereoselective protocol for intermolecular Rh-2(S-PTTL)(4)-catalyzed cyclopropanation using alpha-alkyl-alpha-diazoesters. Intermotecular cyclopropanation is selective over two competing intramolecular pathways: C-H insertion and B-hydride elimination. On the basis of density functional theory calculations and the Davies-Singleton model, for cyclopropanation, a model for asymmetric induction is proposed.
引用
收藏
页码:7230 / +
页数:3
相关论文
共 22 条
[11]   Rh-catalyzed intermolecular cyclopropanation with α-alkyl-α-diazoesters:: Catalyst-dependent chemo- and diastereoselectivity [J].
Panne, Patricia ;
DeAngelis, Andrew ;
Fox, Joseph M. .
ORGANIC LETTERS, 2008, 10 (14) :2987-2989
[12]   Rh-catalyzed intermolecular reactions of alkynes with α-diazoesters that possess β-hydrogens:: Ligand-based control over divergent pathways [J].
Panne, Patricia ;
Fox, Joseph M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (01) :22-23
[13]   Asymmetric synthesis of tropanes by rhodium-catalyzed [4+3] cycloaddition [J].
Reddy, Ravisekhara P. ;
Davies, Hum M. L. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (34) :10312-+
[14]   Dirhodium tetracarboxylates derived from adamantylglycine as chiral catalysts for enantioselective C-H aminations [J].
Reddy, Ravisekhara P. ;
Davies, Huw M. L. .
ORGANIC LETTERS, 2006, 8 (22) :5013-5016
[15]   Dirhodium tetracarboxylate derived from adamantylglycine as a chiral catalyst for carbenoid reactions [J].
Reddy, Ravisekhara P. ;
Lee, Gene H. ;
Davies, Huw M. L. .
ORGANIC LETTERS, 2006, 8 (16) :3437-3440
[16]   Enantio- and diastereoselective synthesis of cis-2-aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh(II)-catalyzed C-H insertion process [J].
Saito, H ;
Oishi, H ;
Kitagaki, S ;
Nakamura, S ;
Anada, M ;
Hashimoto, S .
ORGANIC LETTERS, 2002, 4 (22) :3887-3890
[17]   Catalytic enantioselective intermolecular cycloaddition of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkynes and styrenes using chiral dirhodium(II) carboxylates [J].
Shimada, Naoyuki ;
Anada, Masahiro ;
Nakamura, Seiichi ;
Nambu, Hisanori ;
Tsutsui, Hideyuki ;
Hashimoto, Shunichi .
ORGANIC LETTERS, 2008, 10 (16) :3603-3606
[18]   A convenient method for the preparation of (Z)-alpha,beta-unsaturated carbonyl compounds [J].
Taber, DF ;
Herr, RJ ;
Pack, SK ;
Geremia, JM .
JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (08) :2908-2910
[19]   Cyclopentane construction by Rh-catalyzed intramolecular C-H insertion: Relative reactivity of a range of catalysts [J].
Taber, DF ;
Joshi, PV .
JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (12) :4276-4278
[20]   Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate]:: an exceptionally effective Rh(II) catalyst for enantiotopically selective aromatic C-H insertions of diazo ketoesters [J].
Tsutsui, H ;
Yamaguchi, Y ;
Kitagaki, S ;
Nakamura, S ;
Anada, M ;
Hashimoto, S .
TETRAHEDRON-ASYMMETRY, 2003, 14 (07) :817-821