Metal Catalysed Carbon-Carbon Bond-Forming Reactions, Volume 3

by Roberts, Stanley M.; Xiao, Jianliang; Whittall, John; Pickett, Tom E.

• ISBN13: 9780470861998
• ISBN10: 0470861991
• Edition: 1st
• Format: Hardcover
• Copyright: 2004-11-30
• Publisher: WILEY

Summary

The chemist has a vast range of high-tech catalysts to use when working in fine chemical synthesis but the catalysts are generally hard to use and require both time, skill and experience to handle properly. The Catalysts for Fine Chemical Synthesis series contains tested and validated procedures which provide a unique range resources for chemists who work in organic chemistry."... of great value to synthetic organic chemists..." (The Chemists, Summer 2003)Volume 3 in the series focuses on catalysts for carbon-carbon bond formation and presents practical and detailed protocols on how to use sophisticated catalysts by the "inventors" and "developers" who created them. The combination of protocols and review commentaries helps the reader to easily and quickly understand and use the new high-tech catalysts.

Author Biography

Professor S.M. Roberts and Dr Jianliang Xiao, Department of Chemistry, The University of Liverpool, The Robert Robinson Laboratories, Liverpool, UK.

Dr Tom Pickett and Dr John Whittall, Stylacats Ltd, Liverpool University.

Table of Contents

Series Preface	xvii
Preface to Volume 3	xix
Abbreviations	xxi
List of Chemical Names Used	xxiii
1 Considerations of Industrial Fine Chemical Synthesis	1	(12)
Mark W. Hooper	1	(12)
1.1 Introduction
1.2 Types of processes - flow charts	2	(1)
1.2.1 Classical process	2	(1)
1.2.2 General catalytic process	3	(1)
1.3 Costs associated with use of catalysts	3	(9)
1.3.1 Catalyst fabrication costs	3	(3)
1.3.2 Intellectual property right (IPR) issues	6	(1)
1.3.3 Separation costs	7	(1)
1.3.4 Pre-reaction/immobilisation	7	(1)
1.3.5 Post reaction - separation	8	(1)
1.3.6 Industrial examples	9	(3)
References	12	(1)
2 Alkylation and Allylation Adjacent to a Carbonyl Group	13	(22)
2.1 The RuH2(CO)(PPh3)3-catalysed alkylation, alkenylation and arylation of aromatic ketones via carbon-hydrogen bond cleavage
Fumitoshi Kakiuchi, Satoshi Ueno and Naoto Chatani	14	(7)
2.1.1 Preparation of carbonyldihydrotris(triphenylphosphine) ruthenium	14	(2)
2.1.2 Synthesis of 8-(2-triethoxysilanylethyl)-3,4-dihydro-2H-naphthalen-1-one	16	(1)
2.1.3 Synthesis of 8-(1-methyl-2-trimethylsilanylvinyl)-3,4-dihydro-2H-naphthalen-1-one	17	(1)
2.1.4 Synthesis of 1-biphenyl-2-yl-2,2-dimethylpropan-1-one	18	(1)
2.1.5 Conclusion	19	(2)
References	21	(1)
2.2 Catalytic, asymmetric synthesis of α,α-disubstituted amino acids using a chiral copper-salen complex as a phase transfer catalyst
Michael North and Jose A. Fuentes	21	(6)
2.2.1 Synthesis of (chsalen)	22	(1)
2.2.2 Synthesis of copper(II) (chsalen)	23	(1)
2.2.3 Alkylation of alanine methyl ester Schiff base by chiral salen-metal catalysts, α-benzyl-alanine methyl ester	24	(2)
2.2.4 Conclusion	26	(1)
References	27	(1)
2.3 Asymmetric phase-transfer catalysed alkylation of glycine imines using cinchona alkaloid derived quaternary ammonium salts
Barry Lygo and Benjamin I. Andrews	27	(9)
2.3.1 Synthesis of (1S,2S,4S,5R,1'R)-1-(anthracen-9-ylmethyl)-5-ethyl-2-[hydroxy(quinolin-4-yl)methyl]-1-azoniabicyclo[2.2.2]octane bromide	28	(1)
2.3.2 Synthesis of (1S,2S,4S,5R,1'R)-1-(anthracen-9-ylmethyl)-5-ethyl-2-[benzyloxy(quinolin-4-yl)methyl]-1-azoniabicyclo[2.2.2]octane bromide	29	(2)
2.3.3 Synthesis of (2S)-tert-butyl 2-amino-4-bromopent-4-enoate	31	(1)
2.3.4 Conclusion	32	(1)
References	33	(2)
3 Asymmetric Alkylation or Amination of Allylic Esters	35	(24)
3.1 Synthesis and application in palladium-catalysed asymmetric allylic substitution of enantiopure cyclic &beta-iminophosphine ligands
Maria Zablocka, Marek Koprowski, Jean-Pierre Majoral, Mathieu Achard and Gérard Buono	36	(4)
3.1.1 Synthesis of (2,6-dimethyl-phenyl)-(1-phenyl-2,3,3a,8a-tetrahydro-1H-1-phospha-cyclopenta[α]inden-8-ylidene)-amines 1Rp	36	(1)
3.1.2 Synthesis of (E)-Methyl 2-carbomethoxy-3,5-diphenylpent-4-enoate	37	(2)
3.1.3 Synthesis of benzyl(1,3-diphenylprop-2-enyl)amine	39	(1)
3.1.4 Conclusion	40	(1)
References	40	(1)
3.2 (9H,9'H,10H,10'H,11H,11H',13H,13'H,14H,14'H,15H,15'H-perfluorotricosane-12,12'-diyl)bis [(4S)-4-phenyl-2-oxazoline as a ligand for asymmetric palladium-catalysed alkylation of allylic acetates in fluorous media
Jérôme Bayardon and Denis Sinou	40	(7)
3.2.1 Synthesis of 2-iodo-1-(1H,1'H,2H,2'H,3H,3'H-perfluorooctyl)-3-propanol	41	(1)
3.2.2 Synthesis of 3-(1H,1'H,2H,2'H,3H,3'H-perfluorooctyl)-1-propanol	42	(1)
3.2.3 Synthesis of 3-(1H,1'H,2H,2'H,3H,3'H-perfluorooctyl)-1-iodopropane	43	(1)
3.2.4 Synthesis of (9H,9'H,10H,10'H,11H,11'H,13H,13'H,14H,14'H,15H,15'H-perfluorotricosane- 12,12'-diyl)-bis-[(4S)-4-phenyl-2-oxazoline]	44	(1)
3.2.5 Synthesis of (E)-Methyl 2-carbomethoxy-3,5-diphenylpent-4-enoate	45	(1)
3.2.6 Conclusion	46	(1)
References	47	(1)
3.3 Facile synthesis of new axially chiral diphosphine complexes for asymmetric catalysis
Matthias Lotz, Gernot Kramer, Katja Tappe and Paul Knochel	47	(4)
3.3.1 Synthesis of (SFc)-1-[(S)-p-tolylsulfinyl]-2-[(o-diphenylphosphino)phenyl]ferrocene	47	(2)
3.3.2 Synthesis of (SFc)-1-diphenylphosphino-2-[(o-diphenylphosphino)phenyl]ferrocene	49	(1)
3.3.3 Conclusion	50	(1)
References	51	(1)
3.4 Chiral ferrocenyl-imino phosphines as ligands for palladium-catalysed enantioselective allylic alkylations
Pierluigi Barbaro, Claudio Bianchini, Giuliano Giambastiani and Antonio Togni	51	(9)
3.4.1 Synthesis of the precursor (R)-1-[(S)-2-bromoferrocenyl] ethyldiphenylphosphine	52	(1)
3.4.2 Synthesis of key precursor (R)-1-[(S)-2-formylferrocenyl] ethyldiphenylphosphine	53	(1)
3.4.3 Synthesis of (R)-1-[(S)-2-ferrocenylidene-ethyl-iminelethyldiphenyiphosphine	54	(1)
3.4.4 Conclusion	55	(1)
References	56	(3)
4 Suzuki Coupling Reactions	59	(32)
4.1 Palladium-catalysed borylation and Suzuki coupling (BSC) to obtain β-benzo[b]thienyldehydroamino acid derivatives
Ana S. Abreu, Paula M.T. Ferreira and Maria-João R.P. Queiroz	60	(4)
4.1.1 Synthesis of the E and Z isomers of the methyl ester of N-tert-butoxycarbonyl-β-bromodehydroaminobutyric acid	61	(1)
4.1.2 Synthesis of the methyl ester of N-tert-butoxycarbonyl-(Z)-[β-(2,3,7-trimethylbenzo[b]thien-6-yl]dehydro-aminobutyric acid	62	(2)
4.1.3 Conclusion	64	(1)
References	64	(1)
4.2 Palladium-catalysed cross-coupling reactions of 4-tosylcoumarins and arylboronic acids: synthesis of 4-arylcoumarin compounds
Jie Wu, Lisha Wang, Reza Fathi and Zhen Yang	64	(3)
4.2.1 Synthesis of 4-tosylcoumarins	65	(1)
4.2.2 Synthesis of 4-arylcoumarin	65	(1)
4.2.3 Conclusion	66	(1)
References	66	(1)
4.3 Cyclopropyl arenes, alkynes and alkenes from the in situ generation of B-cyclopropyl-9-BBN and the Suzuki-Miyaura coupling of aryl, alkynyl and alkenyl bromides
Ramon E. Huertas and John A. Soderquist	67	(3)
4.3.1 Synthesis of 4-cyclopropylbenzaldehyde	67	(2)
4.3.2 Conclusion	69	(1)
References	69	(1)
4.4 One-pot synthesis of unsymmetrical 1,3-dienes through palladium-catalysed sequential borylation of a vinyl electrophile by a diboron and cross-coupling with a distinct vinyl electrophile
Tatsuo Ishiyama and Norio Miyaura	70	(4)
4.4.1 Synthesis of 2-(1-cyclopentenyl)-1-decene	70	(3)
4.4.2 Conclusion	73	(1)
References	74	(1)
4.5 Pd(OAc)2/2-Aryl oxazoline catalysed Suzuki coupling reactions of aryl bromides and boronic acids
Bin Tao and David W. Boykin	74	(3)
4.5.1 Synthesis of 4-methoxybiphenyl	75	(1)
4.5.2 Conclusion	76	(1)
References	77	(1)
4.6 Palladium-catalysed reactions of haloaryl phosphine oxides: modular routes to functionalised ligands
Colin Baillie, Lijin Xu and Jianliang Xiao	77	(4)
4.6.1 Synthesis of 2-diphenylphosphinyl-2'-methoxybiphenyl via Suzuki coupling	78	(1)
4.6.2 Synthesis of 2-diphenylphosphino-2'-methoxybiphenyl	79	(1)
4.6.3 Conclusion	80	(1)
References	80	(1)
4.7 Bulky electron rich phosphino-amines as ligands for the Suzuki coupling reaction of aryl chlorides
Matthew L. Clarke and J. Derek Wool/ins	81	(5)
4.7.1 Synthesis of N-di-isopropylphosphino-N-methyl piperazine	82	(1)
4.7.2 Suzuki coupling reactions using isolated ligand and Pd2dba3.CHCl3 as catalyst	83	(1)
4.7.3 In situ ligand preparation and application in Suzuki coupling of 3-fluorobenzene with phenylboronic acid	84	(1)
4.7.4 Conclusion	85	(1)
References	85	(1)
4.8 Arylation of ketones, aryl amination and Suzuki-Miyaura cross coupling using a well-defined palladium catalyst bearing an N-heterocyclic carbene ligand
Nicholas Marion, Oscar Navarro, Roy A. Kelly III and Steven P. Nolan	86	(6)
4.8.1 Synthesis of 1,2-diphenyl-ethanone by ketone arylation	86	(2)
4.8.2 Synthesis of dibutyl-p-tolyl-amine by aryl amination	88	(1)
4.8.3 Synthesis of 4-methoxybiphenyl	89	(1)
4.8.4 Conclusion	90	(1)
References	90	(1)
5 Heck Coupling Reactions	91	(22)
5.1 Palladium-catalysed multiple and asymmetric arylations of vinyl ethers carrying co-ordinating nitrogen auxiliaries: synthesis of arylated ketones and aldehydes
Peter Nilsson and Mats Larhed	92	(8)
5.1.1 Triarylation: synthesis of N,N-dimethyl-2-[1,2,2-(triaryl) ethenyloxylethanamines with subsequent hydrolysisfurnishing 1,2,2-triaryl ethanones, Table 5.1	92	(3)
5.1.2 Terminal diarylation: synthesis of N,N-dimethyl-2-[2,2-diarylethenyloxy]ethanamine with subsequent hydrolysis furnishing diary] ethanals Table 5.2	95	(2)
5.1.3 Asymmetric Heck arylation: synthesis of 2-aryl-2-methylcyclopentanone	97	(2)
Conclusion	99	(1)
References	99	(1)
5.2 Palladium-catalysed highly regioselective arylation of electron-rich olefins
Lijin Xu, Jun Mo and Jianliang Xiao	100	(4)
5.2.1 Synthesis of 1-acetonaphthone	100	(2)
5.2.2 Synthesis of 3-acetylbenzonitrile	102	(2)
Conclusion	104	(1)
References	104	(1)
5.3 1-[4-(S)-tert-Butyl-2-oxazolin-2-yl]-2-(S)-(diphenylphosphino) ferrocene as a ligand for the palladium-catalysed intermolecular asymmetric Heck reaction of 2,3-dihydrofuran
Tim G. Kilroy, Yvonne M. Malone and Patrick J. Guiry	104	(9)
5.3.1 Synthesis of N-[1-(S)-(Hydroxymethyl)-2,2-dimethylpropyl]ferrocenecarboxamide	106	(1)
5.3.2 Synthesis of [4-(S)-tert-butyl-2-oxazolin-2-yl] ferrocene	107	(1)
5.3.3 Synthesis of 1-[4-(S)-tert-butyl-2-oxazolin-2-yl]-2-(S)-(diphenylphosphino)ferrocene	108	(2)
5.3.4 Asymmetric phenylation of 2,3-dihydrofuran	110	(2)
Conclusion	112	(1)
References	112	(1)
6 Sonogashira Coupling Reactions	113	(14)
6.1 Nonpolar biphasic catalysis: Suzuki- and Sonogashira coupling reactions
Anupama Datta and Herbert Plenio	113	(3)
6.1.1 Nonpolar biphasic Sonogashira reaction of 4-bromoaceto-phenone and phenylacetylene to 1-(4-phenylethynyl-phenyl)-ethanone	114	(1)
6.1.2 Nonpolar biphasic Suzuki reaction for the synthesis of1-biphenyl-4-yl-ethanone	115	(1)
Conclusion	116	(1)
References	116	(1)
6.2 Polystyrene-supported soluble palladacycle catalyst as recyclable catalyst for Heck, Suzuki and Sonogashira reactions
Chih-An Lin and Fen-Tair Luo	116	(12)
6.2.1 Synthesis of 3-bromo-4-methylacetophenone	117	(1)
6.2.2 Synthesis of 1-(3-bromo-4-methyl-phenyl)-ethanol	118	(2)
6.2.3 Synthesis of 3-bromo-4-methyl-styrene	120	(1)
6.2.4 Synthesis of 3-(diphenylphosphino)-4-methyl-styrene	121	(1)
6.2.5 Synthesis of trans-di(μ-acetato)-bis[3-(diphenylphos-phino)-4-styryl]dipalladium(II)	122	(1)
6.2.6 Synthesis of polymer-supported palladacycle catalyst	123	(1)
6.2.7 Synthesis of 1-[4-(2-phenylethynyl)phenyl]ethan-1-one via Sonogashira reaction by the use of polymer-supported palladacycle catalyst	124	(1)
Conclusion	125	(1)
Reference	125	(2)
7 Cross-Coupling Reactions	127	(28)
7.1 Cross-coupling reaction of alkyl halides with Grignard reagents in the presence of 1,3-butadiene catalysed by nickel, palladium, or copper
Jun Terao and Nobuaki Kambe	128	(5)
7.1.1 Synthesis of nonylcyclopropanc	128	(2)
7.1.2 Synthesis of 4-bromo-hexylbenzene	130	(1)
7.1.3 Synthesis of 1,1-diphenyl-1 nonene	131	(1)
Conclusion	132	(1)
References	132	(1)
7.2 Triorganoindium compounds as efficient reagents for palladium-catalysed cross-coupling reactions with aryl and vinyl electrophiles
Luis A. Sarandeses and José Pérez Sestelo	133	(5)
7.2.1 Preparation of triphenylindium	134	(1)
7.2.2 Synthesis of 4-acetylbiphenyl	134	(2)
7.2.3 Synthesis of 1,3-diphenyl-2-propen-1-one	136	(1)
Conclusion	137	(1)
References	138	(1)
7.3 Cross-coupling reactions catalysed by heterogeneous nickel-on-charcoal
Bryan A. Frieman and Bruce H. Lipshutz	138	(9)
7.3.1 Preparation of the heterogeneous catalyst: nickel-on-charcoal	139	(1)
7.3.2 Ni/C-catalysed Suzuki couplings: 2-cyanobiphenyl	140	(1)
7.3.3 Ni/C-catalysed aromatic aminations: N-(4-cyanophenyl)-morpholine	141	(1)
7.3.4 Ni/C-catalysed cross-couplings en route to allylated aromatics: toluene-4-sulfonic acid 2-(3,7,11,15,19,23,27,31, 35,39-decamethyltetraconta-2,6, 10,14,18,22,26,-30, 34,38-decaenyl)-5,6-dimethoxy-3-methylphenyl ester (coenzyme Q10 precursor)	142	(2)
7.3.5 Ni/C-catalysed reductions of aryl chlorides	144	(1)
7.3.6 Microwave assisted Ni/C-catalysed cross coupling of vinyl zirconocenes and aryl halides: 1-octenyl-4-trifluoromethylbenzene	145	(2)
Conclusion	147	(1)
References	147	(1)
7.4 Carbon-carbon bond formation using arylboron reagents with rhodium(I) catalysts in aqueous media
John Mancuso, Masahiro Yoshida and Mark Lautens	147	(9)
7.4.1 Synthesis of (E)-2-[2-(2-methylphenyl)-1- hexenyl]pyridine	148	(1)
7.4.2 Synthesis of methyl (2EZ)-3-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]acrylate	149	(2)
7.4.3 Synthesis of methyl (1 S*,4R*,4aS*,9S*,9aS*)-2,3,4,4a,9,9ahexahydro-1H-1,4-methano-fluoren-9-ylacetate	151	(2)
References	153	(2)
8 Regioselective or Asymmetric 1,2-Addition to Aldehydes	155	(14)
8.1 Development of a highly regioselective metal-mediated allylation reaction in aqueous media
Kui-Thong Tan, Shu-Sin Chng, Hin-Soon Cheng and Teck-Peng Loh	156	(5)
8.1.1 Synthesis of 1-cyclohexylpent-3-en-ol using indium-mediated allylation	156	(1)
8.1.2 Synthesis of 1-cyclohexylpent-3-en-ol using tin-mediated allylation	157	(2)
8.1.3 Synthesis of 1-cyclohexylpent-3-en-ol usingzinc-mediated allylation	159	(1)
Conclusion	160	(1)
References	161	(1)
8.2 Boronic acids as aryl source for the catalysed enantioselective aryl transfer to aldehydes
Jens Rudolph and Carsten Bolm	161	(3)
8.2.1 Preparation of (S)-4-tolyl-phenyl methanol	161	(2)
Conclusion	163	(1)
References	163	(1)
8.3 Jacobsen's Salen as a chiral ligand for the chromium-catalysed addition of 3-chloro-propenyl pivalate to aldehydes: a catalytic asymmetric entry to syn-alk-l-ene-3,4-diols
Marco Lombardo, Sebastiano Licciulli, Stefano Morganti and Claudio Trombini	164	(5)
8.3.1 Synthesis of 3-chloro-propenyl pivalate	165	(1)
8.3.2 Synthesis of alk-1-ene-3,4-diols: Salen-Cr(II) catalysed addition of 3-chloro-propenyl pivalate to cyclohexanecarboxaldehyde	166	(2)
Conclusion	168	(1)
References	168	(1)
9 Olefin Metathesis Reactions	169	(12)
9.1 Highly active ruthenium (pre)catalysts for metathesis reactions
Syuzanna Harutyunyan, Anna Michrowska and Karol Grela	169	(5)
9.1.1 Synthesis of the ruthenium (pre)catalyst	170	(1)
9.1.2 Synthesis of 1-[(4-methylphenyl)sulfonyl]-2,3,6,7-tetrahydro-1H-azepine	171	(1)
Conclusion	172	(1)
References	173	(1)
9.2 A highly active and readily recyclable olefin metathesis catalyst
Stephen J. Connon, Aideen M. Dunne and Siegfried Blechert	174	(4)
9.2.1 Synthesis of polymer supported catalyst (3)	174	(2)
9.2.2 Ring-closing metathesis of an acyclic diene and subsequent catalyst recovery/reuse	176	(1)
Conclusion	177	(1)
References	177	(1)
9.3 Stereoselective synthesis of L-733,060
G. Bhaskar and B. Venkateswara Rao	178	(4)
9.3.1 Synthesis of (2S,3S)-N-tert-butoxycarbonyl-2-phenyl 1,2,3,6-tetrahydro-3-pyridinol	179	(1)
Conclusion	180	(1)
References	180	(1)
10 Cyclisation Reactions	181	(20)
10.1 Molecular sieves as promoters for the catalytic Pauson-Khand reaction
Jaime Blanco-Urgoiti, Gema Dominguez and Javier Pérez-Castells	182	(3)
10.1.1 Synthesis of 3aS*,5R*-5-hydroxy-3,3a,4,5-tetrahydrocyclopenta[a]naphthalen-2-one	182	(3)
Conclusion	185	(1)
References	185	(1)
10.2 Palladium(II)-catalysed cyclization of alkynes with aldehydes, ketones or nitriles initiated by acetoxypalladation of alkynes
Ligang Zhao and Xiyan Lu	185	(5)
10.2.1 Synthesis of 3-phenyl-3-hydroxy-4-(1'-acetoxyhexylidene)tetrahydrofuran	186	(1)
10.2.2 Synthesis of dimethyl 3-acetylamino-4-butyrylcyclo-pent-3-ene-1,1-dicarboxylate	187	(1)
Conclusion	188	(2)
References	190	(1)
10.3 Rhodium(I)-catalysed intramolecular alder-ene reaction and syntheses of functionalised a-methylene-y-butyrolactones and cyclopentanones
Minsheng He, Aiwen Lei and Xumu Zhang	190	(3)
10.3.1 Synthesis of (4-benzylidene-5-oxo-tetrahydro-furan-3-yl)-acetaldehyde	190	(1)
10.3.2 Synthesis of (3-oxo-2-pentylidene-cyclopentyl)-acetaldehyde	191	(1)
References	192	(1)
10.4 Rhodium-catalysed [2+2+2] cyclotrimerisation in an aqueous-organic biphasic system
Hiroshi Shinokubo and Koichiro Oshima	193	(3)
10.4.1 In situ preparation of a water-soluble rhodium catalyst from [RhCl(COD)]2 and trisodium salt of tris(m-sulfonatophenyl)phosphine (tppts)	193	(1)
10.4.2 Synthesis of 1,3,6,8,9,10,11,12,13-nonahydro-2,7-dioxacyclodeca[e]indene	194	(1)
Conclusion	195	(1)
References	196	(1)
10.5 Titanocene-catalysed transannular cyclisation of epoxygermacrolides: enantiospecific synthesis of eudesmanolides
Antonio Rosales, Juan M. Cuerva and J. Enrique Oltra	196	(6)
10.5.1 Preparation and titanocene-catalysed cyclization of epoxygermacrolide: synthesis of (+)-11β13-dihydroreynosin	197	(1)
10.5.2 Titanocene-catalysed cyclization of epoxygermacrolide in aqueous medium	198	(1)
References	199	(2)
11 Asymmetric Aldol and Michael Reactions	201	(24)
11.1 Direct catalytic asymmetric aldol reaction of a α-hydroxyketone promoted by an Et2Zn/linked-BINOL complex
Masakatsu Shibasaki, Shigeki Matsunaga and Naova Kumagai	202	(6)
11.1.1 Synthesis of (2R,3S)-2,3-dihydroxy-1-(2-methoxyphenyl)-5-phenyl-1-pentanone by the first generation Et2,Zn/Linked-BINOL = 2/1 complex	203	(2)
11.1.2 Synthesis of (2R,3S)-3-cyclohexyl-2,3-dihydroxy-1-(2-methoxyphenyl)-1-propanone by the second generation Et7Zn/linked-BINOL = 4/1 complex with MS3A	205	(2)
Conclusion	207	(1)
References	208	(1)
11.2 Highly enantioselective direct aldol reaction catalysed by a novel small organic molecule
Zhuo Tang, Liu-Zhu Gong, Ai-Qiao Mi and Yao-Zhong Jiang	208	(2)
11.2.1 Synthesis of (S,S,S)-pyrolidine-2-carboxylic acid (2'-hydroxyl-1',2'-diphenyl-ethyl)-amine (1)	208	(1)
11.2.2 Direct aldol reaction	209	(1)
Reference	210	(1)
11.3 Direct catalytic asymmetric Michael reaction of α-hydroxyketone promoted by Et2Zn/linked-BINOL complex
Masakatsu Shibasaki, Shigeki Matsunaga and Naova Kumagai	210	(6)
11.3.1 Synthesis of (2R)-2-hydroxy-1-(2-methoxyphenyl)-1,5-hexanedione by the first generation Et,Zn/linked-BINOL = 2/1 complex	211	(2)
11.3.2 Synthesis of (2R)-2-hydroxy-1-(2-methoxyphenyl)-1,5-hexanedione by the second Et2Zn/linked-BINOL 4/1 complex with MS 3A	213	(32)
Conclusion	245
References	215	(1)
11.4 Catalytic enantioselective Michael reaction catalysed by well-defined chiral ruthenium-amido complexes
Masahito Watanabe, Kunihiko Murata, and Takao Ikariya	216	(10)
11.4.1 Synthesis of Ru[(R,R)-Tsdpenl(η6-arenc): Ru[(R,R;-Tsdpen](ρ-cymene), ((R,R)-TsDPEN = 1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) (p-cymene = η6-1-CH3-4-CH(CH3)2C6H4)8b, Ru[(R,R)-Tsdpen](hmb), and Ru[(R,R)-Msdpen](hmb)	217	(2)
11.4.2 Synthesis of (S)-3-di(methoxycarbonyl)methyl-lcyclopentanone from the Michael reaction of dimethyl malonate and 2-cyclopenten-1-one catalysed by Ru[(R,R)-Tsdpen](hmb)	219	(1)
11.4.3 Synthesis of (S)-3-di(methoxycarbonyl)methyl-lcyclopentanone from the Michael reaction of dimethyl malonate and cyclopentenone catalyzed by Ru[(R,R)-N-Msdpen](hmb)	220	(1)
11.4.4 Synthesis (S)-3-di(methoxycarbonyl)methyl-1-cyclohexanone from the Michael reaction of dimethyl malonate and cyclohexenone catalysed by Ru[(R,R)- Msdpen](hmb)	221	(1)
Conclusion	222	(1)
References	223	(2)
12 Stereoselective Hydroformylation, Carbonylation and Carboxylation Reactions	225	(26)
12.1 Ortho-diphenylphosphanylbenzoyl-(o-DPPB) directed diastereoselective hydroformylation of allylic alcohols
Bernhard Breit	226	(4)
12.1.1 Synthesis of 1RS-(±)-[(1-iso-propyl-2-methyl)prop-2-enyll (2-diphenylphosphanyl)benzoate	227	(1)
12.1.2 Synthesis of (1R*,2R*)-(±)-[(1-Isopropyl-4-oxo-2-methyl)butyl] (2-diphenylphosphanyl)-benzoate	228	(1)
Conclusion	229	(1)
References	230	(1)
12.2 The synthesis and application of ESPHOS: A new diphosphorus ligand for the hydroformylation of vinyl acetate
Martin Wills and Simon W. Breeden	230	(8)
12.2.1 Synthesis of ortho-diazobromobenzene	232	(1)
12.2.2 Synthesis of ortho-(dichlorophosphine) bromobenzene	232	(1)
12.2.3 Synthesis of ortho-bis(dimethylamino) bromobenzene	233	(1)
12.2.4 Synthesis of 1,2-bis(dimethylaminophosphanyl)benzene	234	(1)
12.2.5 Synthesis of ESPHOS (1)[²]	235	(1)
12.2.6 Hydroformylation of vinyl acetate[³]	236	(1)
Conclusion	237	(1)
References	237	(1)
12.3 Platinum-catalysed asymmetric hydroformylation of styrene
Submitted by Stefánia Cserépi-Szücs and József Bakos	238	(6)
12.3.1 Rhodium-catalysed asymmetric hydroformylation of styrene	239	(1)
12.3.2 Synthesis of (4R,6R)-4,6-di methyl-2-chloro-1,3,2-dioxaphosphorinane	240	(1)
12.3.3 Synthesis of (2R,4R)-2,4-bis[(4R,6R)-4,6-dimethyl-1,3,2-dioxaphos-phorinane-2-yloxy]-pentane	241	(2)
12.3.4 Determinataion of optical purity: synthesis of mixture of 2-phenylpropionic acid and 3-phenylpropionic acid	243	(1)
12.4 Phosphine-free dimeric palladium (II) complex for the carbonylation of aryl iodides
C. Ramesh, Y. Kubota and Y. Sugi	244	(3)
12.4.1 Synthesis of the dimeric oximepalladacycle	244	(1)
12.4.2 Synthesis of phenyl biphenyl-4-carboxylatc	245	(2)
Conclusion	247	(1)
Reference	247	(1)
12.5 Carboxylation of pyrrole to pyrrole-2-carboxylate by cells of Bacillus megaterium in supercritical carbon dioxide
Tomoko Matsuda, Tadao Harada, Toru Nagasawa and Kaoru Nakamura	247	(4)
12.5.1 Construction of supercritical carbon dioxide reaction system	248	(1)
12.5.2 Carboxylation of pyrrole to pyrrole-2-carboxylate	249	(1)
Conclusion	250	(1)
References	250	(1)
Index	251