Asymmetric synthesis of axially chiral biaryls by nickel-catalyzed grignard cross-coupling of dibenzothiophenes

被引：63

作者：

Cho, YH ^{[1
]}

Kina, A ^{[1
]}

Shimada, T ^{[1
]}

Hayashi, T ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Sci, Dept Chem, Kyoto 6068502, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 11期

关键词：

D O I：

10.1021/jo035880p

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Catalytic asymmetric Grignard cross-coupling of 1,9-disubstituted dibenzothiophenes (6a-c) and dinaphthothiophene (6d) with aryl- and alkyl-Grignard reagents (7) proceeded with high enantio-selectivity (up to 95% ee) in the presence of a nickel catalyst (3-6 mol %) coordinated with 2-diphenylphosphino-1,1'-binaphthyI (H-MOP) or oxazoline-phosphine ligand (i-Pr-phox) in THF to give 2-mereapto-2'-substituted-1,1'-biphenyls (8a-c) and 2-mereapto-2'-substituted-1,1'-binaphthyls (8d) in high yields. The mercapto group in the axially chiral cross-coupling products was converted into several functional groups by way of the methylsulfinyl group. The rate of flipping in dinaphthothiophene was measured by variable-temperature P-31 NMR analysis of methylphenylphosphinyldinaphthothiophene derivative (21).

引用

页码：3811 / 3823

页数：13

共 77 条

[1] Synthesis of an octahydro-1,1′-binaphthyl thioether ligand and comparison with unhydrogenated binaphthyl analogues [J].

Albrow, V ;

Biswas, K ;

Crane, A ;

Chaplin, N ;

Easun, T ;

Gladiali, S ;

Lygo, B ;

Woodward, S .

TETRAHEDRON-ASYMMETRY, 2003, 14 (18) :2813-2819

[2] Catalytic asymmetric oxidative couplings of 2-naphthols by tridentate N-ketopinidene-based vanadyl dicarboxylates [J].

Barhate, NB ;

Chen, CT .

ORGANIC LETTERS, 2002, 4 (15) :2529-2532

[3] HYDRODESULFURIZATION (HDS) MODEL SYSTEMS - OPENING, HYDROGENATION, AND HYDRODESULFURIZATION OF DIBENZOTHIOPHENE (DBT) AT IRIDIUM - FIRST CASE OF CATALYTIC HDS OF DBT IN HOMOGENEOUS PHASE [J].

BIANCHINI, C ;

JIMENEZ, MV ;

MELI, A ;

MONETI, S ;

VIZZA, F ;

HERRERA, V ;

SANCHEZDELGADO, RA .

ORGANOMETALLICS, 1995, 14 (05) :2342-2352

[4] Opening and hydrogenation of dinaphtho[2,1-b:1',2'-d]thiophene (DNT) by soluble rhodium iridium complexes. Homogeneous hydrogenolysis of DNT to 1,1'-binaphthalene-2-thiol by rhodium catalysis [J].

Bianchini, C ;

Fabbri, D ;

Gladiali, S ;

Meli, A ;

Pohl, W ;

Vizza, F .

ORGANOMETALLICS, 1996, 15 (21) :4604-4611

[5] SOME COMPLEXES OF DITERTIARY PHOSPHINES WITH NICKEL(2) AND NICKEL(3) [J].

BOOTH, G ;

CHATT, J .

JOURNAL OF THE CHEMICAL SOCIETY, 1965, (MAY) :3238-&

[6] Novel concepts in directed biaryl synthesis, part 102. The directed synthesis of axially chiral ligands, reagents, catalysts, and natural products through the 'lactone methodology' [J].

Bringmann, G ;

Tasler, S ;

Pfeifer, RM ;

Breuning, M .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 661 (1-2) :49-65

[7] Novel concepts in directed biaryl synthesis, part 101. The lactone concept-a novel approach to the metal-assisted atroposelective construction of axially chiral biaryl systems [J].

Bringmann, G ;

Breuning, M ;

Pfeifer, RM ;

Schenk, WA ;

Kamikawa, K ;

Uemura, M .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 661 (1-2) :31-47

[8] Novel concepts in directed biaryl synthesis, part 78. The lactone concept: An efficient pathway to axially chiral natural products and useful reagents [J].

Bringmann, G ;

Breuning, M ;

Tasler, S .

SYNTHESIS-STUTTGART, 1999, (04) :525-558

[9] A HIGHLY STEREOSELECTIVE SYNTHESIS OF "S(-)-[1,1'-BINAPHTHALENE]-2,2'-DIOL [J].

BRUSSEE, J ;

JANSEN, ACA .

TETRAHEDRON LETTERS, 1983, 24 (31) :3261-3262

[10] ON THE MECHANISM OF THE FORMATION OF "S(-)-(1,1'-BINAPHTHALENE)-2,2'-DIOL VIA COPPER(II)AMINE COMPLEXES [J].

BRUSSEE, J ;

GROENENDIJK, JLG ;

TEKOPPELE, JM ;

JANSEN, ACA .

TETRAHEDRON, 1985, 41 (16) :3313-3319

← 1 2 3 4 5 6 7 8 →