Multicomponent reactions - Zhu.pdf - Index of

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R1 CO2Me NH2 R2 + NHCbz CO2H R1 MeO2C N R O H N S 2 Tos–C H2NC CHO NHCbz O O O R2 R Yield [%] (S) : (R) H 72 42 : 58 H 84 19 : 81 i-Pr 76 19 : 81 H 78 23 : 77 H 59 30 : 70 1 MeOH (C= 0.66 M) 20°C Me i-Pr i-Pr Bn t-Bu R N CO2Me H H 1 mechanisms A or C (R 1 H H O N OMe R bulkier than CO2Me) attack from top face H 1 (R) (R) mechanisms A or C H 33 attack from top face 34 Cl Cl R 1 35 CO2H NO 2 CHO R 2 Bn Et i-Pr-CH2 Me 4-(HO)C6H4CH2 Me MeSCH2CH2 Me Scheme 1.15 H 2N R 1 1.4.3 Chiral Isocyanides, Carboxylic Acids and Carbonyl Compounds NC O OR 2 Yield (35) [%] 61 49 71 64 (S) : (R) < 5 : 95 < 5 : 95 9 : 91 < 5 : 95 1.4 Asymmetric Intermolecular Ugi Reactions 13 C 6 H 11 HNOC Cl NO2 36 As already mentioned in Section 1.4.1, chiral isocyanides usually give no induction at all in Ugi reactions. For example, when using chiral a-substituted or a,adisubstituted isocyanoacetates [7, 27, 44], the two resulting diastereoisomers are 37 O N H N N R 1 C6H11HNOC O O C 6 H 4 Cl CO2R 2 Fe, AcOH C 6 H 4 Cl R 1
14 1 Asymmetric Isocyanide-based MCRs typically obtained in a 1:1 ratio. Even isonitrile 11 (Scheme 1.4), which affords excellent stereoselectivity in the Passerini reaction, is totally inefficient in asymmetric Ugi reaction and this fact has led the authors of that paper to suggest that the isocyanide may not be involved in the step that determines the configuration of the new stereocenter [14]. Finally, even isocyanoglucoses, despite their steric biases, only afforded stereoselectivity of between 50:50 and 57:43 in Ugi condensations with achiral aldehydes, amines and carboxylic acids [45]. At present no chiral carboxylic acid capable of significantly controlling the stereochemistry of the new stereogenic center has been reported [42, 46]. In most cases chiral carbonyl compounds also afford low stereoselectivity. As for the related Passerini reaction, even the use of aldehydes that are known to give excellent asymmetric induction in the reaction with other kinds of C-nucleophiles, results in low or moderate diastereoisomeric ratios. For example, both norbornyl aldehyde 39 [47] and a-alkoxyaldehyde 40 [3, 48] gave drs lower than 2:1 (Scheme 1.16). The same happens with ortho-substituted chromium complex 41 [49], which usually leads to very high asymmetric induction in other nucleophilic additions. Finally, b-substituted aldehyde 42 [50] gave poor results as well. OHC 39 d.r.: 63 : 37 BnO BnO NHBoc CHO 43 45 Scheme 1.16 OBn NH 2 O OBn O 2N + CHO OBn CHO 40 d.r.: 58 : 42 CO 2H F CN CO 2Me CO2H MeO (CO)3Cr Bn–NH 2 H O Protected a-aminoaldehydes follow the same trend, although a notable exception is represented by the reaction of compound 43 with a bulky isonitrile, affording 44 in a 3:1 ratio (the relative configuration of the major product was not determined) [51]. BnO BnO NC OBn BocNH O 41 OBn O d.r.: 80 : 20 d.r.: 55 : 45 Bn O 2N N N O O N H O N H F CCl 3 42 d.r.: 55 : 45 44 d.r.: 75 : 25 CO 2Me CHO
Page 1 and 2: Multicomponent Reactions. Edited by
Page 3 and 4: Multicomponent Reactions Edited by
Page 5 and 6: Contents Preface xiii Contributors
Page 7 and 8: 2.3.4.2 Bycyclic Systems by Ugi-4CR
Page 9 and 10: 8.3.1.5 Palladium-mediated Reaction
Page 11 and 12: 12.5.1 Cyclic Ethers 364 12.5.2 Lac
Page 13 and 14: XIV Preface entities, and the avail
Page 15 and 16: XVI List of Contributors Stefano Ma
Page 17 and 18: 2 1 Asymmetric Isocyanide-based MCR
Page 25 and 26: 10 1 Asymmetric Isocyanide-based MC
Page 27: 12 1 Asymmetric Isocyanide-based MC
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Page 55 and 56: Ph R1 R N H 2 Boc MeO 2C NC MeO 2C
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64 2 Post-condensation Modification
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76 3 The Discovery of New Isocyanid
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HOOC 84 3 The Discovery of New Isoc
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COOMe COOMe 88 3 The Discovery of N
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MeOOC NC MeOOC N H N N + NH 2 S 90
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96 4 The Biginelli Reaction the syn
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98 4 The Biginelli Reaction least 1
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Me Fe 100 4 The Biginelli Reaction
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102 4 The Biginelli Reaction Lewis
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104 4 The Biginelli Reaction One ot
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HO HO H EtO2C Me EtO 2C 106 4 The B
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108 4 The Biginelli Reaction O O Ph
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110 4 The Biginelli Reaction i-PrO
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112 4 The Biginelli Reaction i-PrO
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114 4 The Biginelli Reaction 4.9 Co
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116 4 The Biginelli Reaction 65 Y.
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118 4 The Biginelli Reaction 133 M.
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120 4 The Biginelli Reaction 196 D.
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122 5 The Domino-Knoevenagel-hetero
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D-glucose O O 128 5 The Domino-Knoe
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Ph 132 5 The Domino-Knoevenagel-het
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MeO MeO 146 5 The Domino-Knoevenage
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OMe H MeO rac-154 148 5 The Domino-
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169 150 5 The Domino-Knoevenagel-he
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O (MeO) 2P 183 OEt 88a X + O 183a:
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170 6 Free-radical-mediated Multico
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Cl 178 6 Free-radical-mediated Mult
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I 180 6 Free-radical-mediated Multi
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2 184 6 Free-radical-mediated Multi
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Me 3SiO 190 6 Free-radical-mediated
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EtO I O EtO (OC)5Mo O 194 6 Free-ra
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Ph 196 6 Free-radical-mediated Mult
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200 7 Multicomponent Reactions with
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7.3.4 Synthesis of Iminodicarboxyli
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Boc 97 NH NH 2 MeO O (a) Me2C=CHCOC
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R4 R6 R5 R N 1 R2 B R O 5 R OR OR 6
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Ph Finn [66] has reported that when
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Ph NH2 177 Ph Ph Ph O NHBoc 182, 73
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HO O OH 207 220 7 Multicomponent Re
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224 8 Metal-catalyzed Multicomponen
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O 234 8 Metal-catalyzed Multicompon
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278 9 Catalytic Asymmetric Multicom
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O 2N R 1 282 9 Catalytic Asymmetric
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O O 284 9 Catalytic Asymmetric Mult
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R 1 N C N 286 9 Catalytic Asymmetri
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O R 290 9 Catalytic Asymmetric Mult
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300 10 Algorithm-based Methods for
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The most ancient classification con
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O O O O O N H 2 O Br OH O H 2 N OH
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N HO O F O HN N O F Fig. 10.2. Four
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In the second step, the right part
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and reaction time is a combinatoria
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342 12 Multicomponent Reactions in
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398 13 The Modified Sakurai and Rel
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R 410 13 The Modified Sakurai and R
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syn-123 anti-123 420 13 The Modifie
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R OH anti-126 422 13 The Modified S
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HO 428 13 The Modified Sakurai and
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171 OH R O 173 R H R O R 430 13 The
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O R 200 Ph 438 13 The Modified Saku
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454 Index allyl/allylic - alkoxide
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456 Index Brønsted - acids 98 - ba
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458 Index dialkoxydichlorotitanium
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460 Index furo[2,3-b]furan 358 furo
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462 Index 1-isocyano-1-cyclohexene
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464 Index neuropeptide, cyclic 331
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466 Index quinoline 246, 304 quinol
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468 Index tributyltin - enolate 183
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