Modern Organocopper Chemistry

Modern Organocopper Chemistry. Edited by Norbert Krause

Copyright > 2002 Wiley-VCH Verlag GmbH

ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

xi

Preface

‘‘When one equivalent of cuprous iodide was treated with one equivalent of methyllithium the yellow, ether-insoluble product was formed. Both the precipitate and the ether solution gave a negative color test with Michler ketone. . . . However, when one equivalent of cuprous iodide was treated with two equivalents of methyllithium a clear, practically colorless ether solution was formed. This ether solution gave a strong color test.’’

H. Gilman, R. G. Jones, L. A. Woods, ‘‘The Preparation of Methylcopper and some Observations on the Decomposition of Organocopper Compounds’’, J. Org. Chem. 1952, 17, 1630–1634.

Fifty years ago, Gilman and coworkers marked the beginning of the era of organocopper reagents as synthetic tools in organic chemistry by describing the first preparation of an organocuprate, namely lithium dimethylcuprate (Me2CuLi LiI). Nonetheless, it took more than a decade after this discovery until the widespread use of organocuprates was initiated by the seminal work of House, Corey and others. Soon, the synthetic versatility of organocopper compounds and in particular those of cuprates (which in the case of the composition R2CuLi LiX are referred to as Gilman reagents) was exploited and, in its wake, created an abundance of new reagents, methods, and applications.

Notable in this respect are the introduction of heterocuprates, the use of ‘‘dummy ligands’’ in order to improve the ‘‘economy’’ of the reagents, the implementation of ‘‘higher-order’’ and ‘‘lower-order’’ cuprates and the development of chiral organocopper reagents. Last but not least, the refinement of both theoretical and experimental methods (e.g., X-ray, NMR spectroscopy, kinetics) has shed light on the structures of organocopper compounds and the mechanism of their reactions. Although nowadays regarded as indispensable tools in the repertoire of synthetic organic chemists, organocopper chemistry is still a vivid field with numerous new copper-promoted transformations and chiral catalysts being developed over the last years.

This book captures recent advances of organocopper chemistry and serves as a detailed guide to the high standard now reached in the field. Brief summaries of previous achievements as well as thorough discussions of new methods and techniques facilitate (even for students) the entry into Modern Organocopper Chemistry, an area that will certainly witness further exciting discoveries in the near future.

xii Preface

Selected authors, all of them being protagonists in the respective area, provide profound expertise about both experimental and theoretical aspects of coppermediated transformations to a wide range of scientists in academia and industry. Combined with essays about structure and mechanism (chapters 1 and 10), Modern Organocopper Chemistry compiles novel techniques for the generation of functionalized organocopper reagents (chapter 2) and heteroatomas well as heteroatomalkylcuprates (chapter 3). Application of these organometallics in reactions with extended multiple bond systems (chapter 4), in reductions (chapter 5) and in stereoselective conjugate addition and substitution reactions (chapters 6–8), as well as their use for the synthesis of biologically active products (chapter 9), round out this monograph

The idea of this book, bringing together all important aspects of Modern Organocopper Chemistry and presenting them in a prolific way, has emerged over the last years in discussions with many colleagues, students and friends. Here, the European Commission deserves special mention for genereous support of several projects within the framework European Cooperation in the Field of Scientific and Technical Research (COST). I thank the authors of this volume for their determination to complete their contribution in time of the 50th anniversary of Gilman’s groundbreaking discovery. Finally, I dedicate this monograph to the over 2000 scientists mentioned in the author index for their original contributions which made the book possible.

Dortmund, December 2001

Norbert Krause

Modern Organocopper Chemistry. Edited by Norbert Krause Copyright > 2002 Wiley-VCH Verlag GmbH ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

xiii

List of Authors

Leggy A. Arnold

Department of Organic and Molecular

Inorganic Chemistry

Stratingh Institute

University of Groningen

Nijenborgh 4

NL-9747 AG Groningen

The Netherlands

Jan-Erling Ba¨ckvall

Department of Organic Chemistry

Arrhenius Laboratory

Stockholm University

S-10691 Stockholm

Sweden

Bodo Betzemeier

Department Chemie

Ludwig-Maximilians-Universita¨t Mu¨nchen

Butenandtstr. 5–13, Haus F

D-81377 Mu¨nchen

Germany

Bernhard Breit

Institut fu¨r Organische Chemie und Biochemie

Albertstr. 21 D-79104 Freiburg Germany

Yukiyasu Chounan

Department of Natural Science

Faculty of Education

Hirosaki University

Hirosaki 036-8560

Japan

Peter Demel

Institut fu¨r Organische Chemie und Biochemie

Albertstr. 21

D-79104 Freiburg

Germany

R. Karl Dieter

Hunter Laboratory

Department of Chemistry

Clemson University

Clemson, SC 29634-0973

USA

Ben L. Feringa

Department of Organic and Molecular

Inorganic Chemistry

Stratingh Institute

University of Groningen

Nijenborgh 4

NL-9747 AG Groningen

The Netherlands

Anja Ho mann-Ro¨der

Dortmund University

Organic Chemistry II

D-44221 Dortmund

Germany

Rosalinde Imbos

Department of Organic and Molecular

Inorganic Chemistry

Stratingh Institute

University of Groningen

Nijenborgh 4

NL-9747 AG Groningen

The Netherlands

Johann T. B. H. Jastrzebski

Debye Institute

Department of Metal-Mediated Synthesis

Utrecht University

Padualaan 8

NL-3584 CH Utrecht

The Netherlands

xivList of Authors

Sofia E. Karlstro¨m

Department of Organic Chemistry Arrhenius Laboratory

Stockholm University S-10691 Stockholm Sweden

Paul Knochel Department Chemie

Ludwig-Maximilians-Universita¨t Mu¨nchen Butenandtstr. 5–13, Haus F

D-81377 Mu¨nchen Germany

Norbert Krause Organic Chemistry II Dortmund University D-44221 Dortmund Germany

Bruce H. Lipshutz

Department of Chemistry & Biochemistry University of California

Santa Barbara, CA 93106 USA

Seiji Mori

Department of Environmental Sciences Ibaraki University

Mito 310-8512 Japan

Robert Naasz

Department of Organic and Molecular

Inorganic Chemistry

Stratingh Institute

University of Groningen

Nijenborgh 4

NL-9747 AG Groningen

The Netherlands

Eiichi Nakamura

Department of Chemistry

The University of Tokyo

Bunkyo-ku

Tokyo 113-0033

Japan

Gerard van Koten Debye Institute

Department of Metal-Mediated Synthesis Utrecht University

Padualaan 8 NL-3584 CH Utrecht The Netherlands

Yoshinori Yamamoto

Department of Chemistry

Graduate School of Science

Tohoku University

Sendai 980-8578

Japan

Modern Organocopper Chemistry. Edited by Norbert Krause Copyright > 2002 Wiley-VCH Verlag GmbH ISBNs: 3-527-29773-1 (Hardcover); 3-527-60008-6 (Electronic)

369

Subject Index

a

acceptor-substituted dienes
1,4-addition 146
1,6-addition 146
addition, regioselectivity of					145
acceptor-substituted enynes
activation parameters				158
1,4-addition		124, 150, 153
1,6-addition		124f, 150 , 160, 316, 321
anti-Michael addition				153
kinetic measurements				158
mechanism		158f
NMR spectroscopic investigations 158
rate-determining step				158
1,4-reduction		153
1,6-reduction		153
tandem 1,6- and 5,6-addition					151
acceptor-substituted polyenynes
1,8-addition		159, 316
1,10-addition		159f, 316
1,12-addition		159f, 316
acetylenic ethers
polyfunctional			64
acridones	109
a-acyloxycuprates			115
a-acylthiocuprates			115
1,4-addition	53, 124, 188, 289f, 293f, 310,
315, 330, 338, 340; see also respective
substrates and reagents
activation parameters				321
active substrate control				190
acyclic enones			242
aldol reaction		225
auxiliary-controlled 208
BF3 activation		333f
catalytic	129, 133
catalytic cycle		233
CIDNP	320
copper-catalyzed			130, 224, 228 , 234,
236 , 239, 242f, 252, 322

cyclic enones 239
2-cyclopentenone				240f
diastereoselectivity 189 , 198 , 202 ,
208f, 324
directed	200
enantioselectivity				2, 32, 127 , 224 , 229 ,
234, 236 , 239 , 252 , 316f, 322
ESR spectroscopy				320
four-centered mechanisms						318
functionalized organocopper compounds
46, 51, 54, 65f, 68
Grignard reagents				1
kinetic measurements					320f
kinetic isotope e ects					320, 322f, 335
Lewis acid activation					190, 199f, 332
mechanism		38, 233, 315, 318f, 321, 322f,
327
Me3SiCl acceleration					333
nickel-catalyzed			229
NMR spectroscopy				38, 323
passive substrate control						190
rate-determining step					320, 322, 335
rhodium-catalyzed				227, 255
six-centered mechanisms						318
solvent e ects			318
transition states			324
1,6-addition	124f, 150 , 160, 316
diastereoselectivity				158
kinetic isotope e ects					158
Lewis acid activation					153
mechanism		158f, 321
NMR Spectroscopy				158
rate-determining step					158
1,8-addition	159, 316
1,10-addition		159f, 316
1,12-addition		159f, 316
alkenylzirconocenes
cross-coupling			73
a-alkoxyalkenylcuprates
1,4-addition		112

370	Subject Index
	a-alkoxyalkylcuprates				110f, 114f
	1,4-addition		111, 113, 132
	cyclic	111
	enantiomerically pure					111
	isomerization		111
	racemization		111
	a-alkoxyalkyllithium reagents						110
	aldol reactions
	diastereoselectivity				87
	alkenyl cuprate		91
	alkenylcopper compounds
	cyclization 67
	functionalized			52
	alkoxy(alkyl)cuprates
	1,4-addition 127 , 226
	chiral 127 , 226
	dynamic ligand exchange						129
	enantioselectivity 127 , 226
	alkylcopper compounds
	b-elimination		167
	7-[(E)-alkylidene]-cephalosporins 108
	alkynes
	carbocupration			73, 145
	germylcupration			100
	hydrozirconation				71f
	methylalumination				54
	silylcupration		82, 93 , 96
	stannylalumination 54
	stannylcupration				82, 91, 93 , 96 , 99f
	silylmagnesiation				95
	alkynyl epoxides
	kinetic resolution				284f
	alkynylcerium reagent					214
	alkynylcuprate		53f
	5-alkynylidene-1,3-dioxan-4-ones 157
	allenes	150, 153, 155, 172
	chiral	157f
	functionalized			152
	regioselectivity			99
	silylcupration		82, 93, 96, 100
	stannylcupration				82, 93, 99
	sterically encumbered					152, 156
	b-allenic esters		152, 154
	allenic amino acids				157
	allenic copper(III) intermediate
	reductive elimination					158
	allenic natural products					156
	allenolate 325
	protonation		91
	allenyl amines		121
	allenyl enolate		150, 154
	aldol reactions			156
	carbometalation			151
	electrophilic trapping					155

oxidation	156
protonation		154f
allenylketene acetals				155f
allenylphosphine oxide 325
allylic substititon			see SN 2 0 substitution
allyl thioethers
SN20 substitution				266
allylcuprate	102
allylic A1;3 strain			85, 193, 196, 198, 213f, 217
allylic carbamates
SN20 substitution				263f
allylic sulfides
SN20 substitution				267
allylic sulfoximines
SN20 substitution				264
ambident enolate			146
ambident substrates				145
amido(alkyl)cuprates				108
1,4-addition		127

chiral 127

intramolecular allylic rearrangement 129

NMR spectroscopy 127
reductive elimination				109
theoretical calculations				127
thermal stability			125
(G)-amijitrienol 92
amino acids
non-protenogenic			107
a-amino acids	99
functionalized		94
a-amino alcohols		107
b-amino alcohols		107
a-aminoalkylcuprates			80, 109, 115
1,2-addition	117
1,4-addition 117
enantiomerically pure				121
substitution reactions				118
thermal stability			119
a-aminoalkylstannanes
1,4-addition	115
7-aminocephalosporanic acid 300
anhydroretinols	100
annulation
enantioselectivity			252
antiestrogens	148

( )-aristermycin 110 arylchromium enone complex

planar chiral	209
arylcopper compounds
functionalized 2, 16, 46, 49f
arylcuprates
aggregation	28

molecular weight determination 27 NMR spectroscopy 27

a-arylselenoalkylcuprates 114
a-arylthiocuprates 115
aurodox	100
axial chirality 150, 152, 156
aziridines	285f, 300, 305, 327
desymmetrization 285

b

B956	303, 305
B957	303, 305
bafilomycin A1		293
Bartlett pear constituent			147
benzoquinone monoacetals
1,4-addition		247
desymmetrization 247
biaryls	22
atropselective coupling			202
palladium-catalyzed coupling				202
symmetric		4, 16, 25
BINAP	176f, 185, 227, 255
BINOL	230f, 234, 236 , 241 , 282
BIPHEMP 176f
bis(aryl)copper(II) compounds				4
1,2-bis-(diphenylphosphino)ethane (DPPE)
10, 11, 16, 33

bis-(diphenylphosphine)ferrocene (DPPF) 185 bis-(diphenylphosphino)methane (DPPM)

10, 11
bis(mesityl)copper anions 16
bislactim ether		148
boron-zinc exchange			59f, 228f
a-borylalkylcuprates			115
brevetoxin B	296f
bromoallene	305
bromothiophene		50

c

( )-capnellane 84
carbocupration	47, 67, 73, 145, 289, 309,
315f, 323f, 329, 340
four-centered mechanism			325
intramolecular 73
mechanism	325, 327
rate-determination step			326
reductive elimination sequence 73
trap-and bite-mechanism			326
carbolithiation	329
carbacyclin analogues		106
CBS reduction	280
cephalosporin	108, 299
D3-cephems 299f
(G)-chiloscyphone 88
chiral amplification		see non-linear
enantioselectivity

		Subject Index	371
chiral auxiliary	202f, 260, 262f, 268, 271
chirality transfer		213, 263
axis-to-center 156f
chlorotetaine	148
(þ)-compactin	84
p-complex 38, 112, 121, 150, 158, 160, 198.
233, 262, 319f, 321, 323, 336, 338
conjugate addition		see 1,4-addition, 1,6-

addition etc.

conjugate addition and elimination sequence

271
copper
oxidation states				3
copper arenethiolate					9, 23f, 31, 124f, 150,
154
chiral	2, 131, 272, 276
copper benzoate				23
copper boronate				52
copper enolate			169, 176f
copper hydride			167, 169, 171 , 176, 179f,
181f
chiral	177
powder X-ray di raction 1784
transmission electron microscopy							184
copper(I) salts
transmetalation				5
copper(II) salts
oxidizing properties					5
reduction		4
copper(III) intermediate						4 , 123, 131, 153,
262, 270, 319, 323, 328f, 331f, 336
reductive elimination						158, 160
copper-carbon bond
kinetic stability of					7
cortisone	334
(G)-crotanecine 95
12-crown-4 34
crown ether		328, 332
(þ)-cucurmene			84
(þ)-a-cuparenone				84
(þ)-b-cuparenone				84
b-cuprio(III) enolate					323
b-cuprio ketone			323
a-cuprio(I) ketone				324
cuprates
chiral	127, 148, 225
in situ regeneration					154
cyanocuprates			26
aggregation			36
EXAFS	36
higher-order			2, 26, 34 , 81, 337f
lower-order		34 , 153, 190, 212, 298, 337
molecular weight determinations							36f
NMR spectroscopy					35f, 81, 337

372	Subject Index
	cyanocuprates (cont.)				functionalized			280
	reactivity	35			preparation		59f
	theoretical studies			337	dipeptide isosteres			305
	XANES	36			ortho-diphenylphosphinobenzoyl (o-DPPB)
	X-ray crystal structure determination 35f,				group	201f
81, 337					a-dithioalkylcuprates
	cyano-Gilman cuprates			37, 109f, 150, 152,	1,4 addition		113
157, 162, 190, 194, 196, 209, 217, 294,					dummy ligand		124, 167, 335f
296, 300, 302, 316, 337					dynemicin	114
	h5-cycloheptadienyliron complexes 63				dysidiolide	298f
	2,5-cyclohexadienone ethers
	1,4-addition		248		e
	2,5-cyclohexadienone monoacetals				eicosanoid	300f
	1,4-addition		248		elaiophylin

2-cyclohexenones 243			electrophiles
kinetic resolution		243	hard	155
cyclosporin A	294		soft	155
			enediynes
d			stannylcupration			96, 100
Davis’ reagent	193f		( )-enterolactone 84
density functional (DFT) calculations 330f			enyne acetates
(þ)-14-deoxyisoamijiol 106			SN200 substitution			161f
deprotonation			enyne oxiranes
asymmetric	121		SN200 substitution			161
des-epoxy-rosaramycin 108			ephedrine		128f
Dewar-Chatt-Duncanson (DCD) complex			(G)-10-epi-elemol 106
321, 325f			epi-widdrol		106
dialkenylchloroboranes			epoxides		see oxiranes, vinyloxiranes
transmetalation		52	EPR spectroscopy			109

a-dialkoxyalkylcopper reagents						ethyl (2E,6Z)-2,6-dodecadienoate 147
1,4-addition		112				ethylenic acetals
4,40-di-t-butylbiphenyl (DTBB)					47	substitution reactions			269
3,4-dichlorocyclobutene-1,2-dione 64						EXAFS (extended X-ray absorption fine
Diels-Alder reactions				162		structure spectroscopy)				3, 36, 39, 318
intramolecular			65, 156, 289
dienyl acetals						f
chiral	161					Felkin-Anh model		192
SN20 substitution				161, 269		ferrocene thioethers		278
SN200 substitution				160, 269		ferrocene thiolates		277
dienylic carbonates						ferrocenes
SN20 substitution				161		chiral	277
dienylic carboxylates						ferrocenylamines 280f
SN20 substitution				160f		chiral	62
SN200 substitution				160f		FK-506 293f
a-dietyopterol		95				a-fluoroalkenylcuprates			122f
(þ)-dihydrocodeinone				106		a-fluoroalkylcuprates 122f
( )-dihydrocodeinone				106, 291		forskolin	289f
2,5-dihydrofurans			157			( )-frontalin 84
(G)-dihydrojasmone				113		frontier molecular orbitals				210f
(G)-dihydronepetalactone 104f						fullerenes	317
dimethyl dioxirane (DMDO)					157
diorganozinc reagents 55						g
chiral	60f					germylcopper reagents
SN20 substitution				62		1,4-addition 92f

		Subject Index	373
germylcuprates		k
1,4-addition 92f		kinetic isotope e ects 130, 158, 317, 320,
SN2 substitution	106f	322f, 331, 335
SN20 substitution 106f		Kocienski rearrangement 306
Gilman cuprates	1, 26, 109, 145, 147, 152f,
167, 259, 295, 316, 337		l
gold(III) chloride	157	b-lactams 295f, 299
Grignard reagents		lactones

functionalized 47			1,4-addition 250
Grubb’s catalyst	253		(þ)-lanostenol 106
			leaving group
h			chiral 218, 262
Hajos-Parrish annulation		252	[5-13C]-leucine 208
halogen-magnesium exchange 47 , 58			ligand-accelerated catalysis 227, 230 , 283
Heck reactions	95		localized molecular orbitals (LMOs) 326
a-heteroarylcuprates 112			logarithmic reactivity profiles 126f
a-heteroarylzinc cuprates		114	lower order cuprates 337
heteroatomalkylcuprates
1,4-addition	127		m
chiral 127			magnesium cuprates

non-transferable ligands

123

X-ray crystal structure determination 30

a-heteroatomalkylcuprates

79f, 109f, 114,

(þ)-magydardiendiol

84

121, 123, 134

( )-malyngolide 84

non-transferable ligands

123, 126

manoalide

306f

heteroatomcuprates

79f, 102, 134

mesitylcopper

12, 16, 23f, 33

chiral

129

metalate rearrangements

108, 289, 306f

hexamethyldisilazidocuprates

126

( )-methylenolactocin 57f

higher order cuprates30, 81, 153, 211f, 306

( )-N-methylephedrine 278

cryoscopy 337

methyl epijasmonate

57f

NMR spectroscopy

337

7a-methylestrone 148

Horner-Wadsworth-Emmons (HWE)

(3S, 4S)-4-methyl-3-heptanol 300f

olefination

202

methyl 2,4,5-tetradecatrienoate 156

HSAB principle

145, 155, 158, 229

(þ)-mevinolin 84

see 1,4-addition, 1,6-addition

hydrido cuprates

167f

Michael addition

in situ generation

172

etc.

1,4-reduction

172

Michael acceptors

hydroalumination

53

extended

146

hydroboration

228f

misoprostol

72

hydroboration/boron-zinc exchange 62

Mitsunobu reaction

292f

hydroformylation

202

molybdenum allyl complexes

hydrosilylation

181

chiral

209

a-hydroxyallenes

157, 284f

(þ)-morphine

106

hygrolidin

293

( )-morphine

106, 290f

Mukaiyama aldol reaction

178

i

multiple bond systems

iminophosphines

243

extended 145 , 160

iodine-zinc exchange

59f

muscone

128, 226, 240

3-iodo-2-indolylcopper 48

iodouracil

47

n

Ireland-Claisen rearrangement

156

natural products

289 ; see individual names

iron complexes

Nazarov cyclization

102

chiral

209

( )-neopanocin A

110

iso[7]-levuglandin D2

195, 294f

nitroalkenes

( )-Isopinocamphenylboran

61

1,4-addition

196, 224, 250f, 255

374Subject Index

3-nitrocoumarins

1,4-addition 251

nonlinear enantioselectivity 128, 131, 234f nontransferable ligands 2, 61, 79f, 108, 123,

126, 134, 167, 224, 272, 335 chiral 224

3-norcephalosporin 172 (G)-norruspoline 119 Nozaki-Hiyama-Kishi reaction 303

o

olivin 193, 195
olivomycin	193
organoaluminium reagents
transmetalation			51, 53f
organoargentates			27
organoaurates		27, 29, 328
organoboron reagents
transmetalation			51
organocopper(I) compounds
aggregation		2f, 7 , 11 , 16 , 25, 37, 225,
316
ate complex		10
autocatalytic decomposition							6
bearing acidic hydrogens						61
bonding	6
bridging groups			17f, 23
charge disproportionation						16
chiral 29, 61
cluster structure			339
coordinating substituents						18, 20, 24
coordination geometries						6f, 14, 18
coordination numbers					6
crystallization		3
decomposition			22, 25
degradation		10
functionalized			45
heteroatom-functionalized						25, 79
heteroleptic		17f, 22f
homoleptic 8, 18
b-hydrogen elimination process								6, 11
incorporation of gold					19
incorporation of silver					19
in syntheses of organotin halides								16
interaggregate exchange						22
intermolecular coordination							14
intramolecular coordination							6, 13
IR spectroscopy			3, 39
kinetically active species						37
Lewis acid-activation					217
molecular orbitals				7, 80, 210f, 326
molecular weight determinations								2,
11
NMR spectroscopy				3, 9, 22, 39

non-transferable ligands					2, 61, 79f, 108,
123, 126, 134, 167, 224, 272, 335
oxidation	5
oxidative decomposition					16
protonolysis		23
reaction with amines				108
resting-state species				3
self-assembly		22, 29
solubility	9, 14, 19
stability	25
stabilization		9f, 13
structure-reactivity relationship						3, 7, 14, 38f
thermal decomposition					11, 16, 23
thermal stability			9, 6, 9, 18
thermodynamic stability					18, 22, 37
three-center, two-electron bonding 2, 7, 13,
16
X-ray crystal structure determination							3 ,
8f, 11f, 17, 19 , 37
organocopper(II) compounds 5
one-electron reduction process						4
oxidizing properties				4f
two-electron reduction process						4
organocuprates
aggregation		19, 30
anionic	32
bridging groups			29
chiral 29
contact ion pairs (CIPs)					38f
p-coordination			33
disproportionation 32, 37
enantiomerically pure					32
heteroleptic		26f, 31
higher order		30, 81, 153, 211f, 306 , 337
homoleptic		26f, 32, 37
kinetically active species					32
molecular weight determination						27
neutral	27
NMR spectroscopy				2, 27, 32, 38
non-transferable ligands					108
orbital interactions				338
solvens-separated ion pairs (SSIPs)							38f
structure-reactivity relationship						26
thermodynamic stability					32
X-ray crystal structure determination							2,
26, 29
organolithium reagents
functionalized			45
transmetalation			45
organomagnesium reagents
functionalized			45, 47
transmetalation			45, 47 , 58
organomanganese reagents
1,4-addition		70f