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Green, Mild and Versatile Synthetic Methods - Aldrichimica Acta Vol. 41 No. 3

Green, Mild and Versatile Synthetic Methods - Aldrichimica Acta Vol. 41 No. 3

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Transition-Metal-Catalyzed Cross-Couplings
Going Green: in Water at Room Temperature
Preparation of Chiral Diamines by the Diaza-Cope Rearrangement (DCR)
Transition-Metal-Catalyzed Cross-Couplings
Going Green: in Water at Room Temperature
Preparation of Chiral Diamines by the Diaza-Cope Rearrangement (DCR)

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Categories:Types, Research, Science
Published by: Sigma Aldrich Chemistry on Feb 11, 2009
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06/11/2013

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GREEN,MILD, AND VERSATILE SYNTHETIC METHODS
VOL. 41, NO. 3 • 2008
Transition-Metal-Catalyzed Cross-CouplingsGoingGreen: in
Water 
at Room TemperaturePreparation of Chiral Diamines by theDiaza-Cope Rearrangement (DCR)
 
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Oxidation Reagent 
The selective oxidation o alcohols under conditions which are environmentallyriendly and/or do not require toxic and hazardous chemicals is a well-precedented problem in organic synthesis. More recently, conditions havebeen developed which use a catalyst system comprised o DABCO
®
-CuCl in the presence o TEMPO and molecular oxygen as the oxidant.This mild catalytic oxidation generates water as the only byproduct.
RR'OHDABCO
-CuCl (5 mol %)TEMPO (5 mol %)O
2
, rt, various solvents*–H
2
ORR'O
703141R = aryl, alkyl; R' = H, alkyl, aryl
*CH
3
NO
2
, 1,4-dioxane, DMF, DMSO, or CH
3
CN24–94%
Mannam, S. et al.
 Adv. Synth. Catal.
 
2007
,
 349
, 2253.
 
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Reagent for the Preparation of Organozincs
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is an exceptional precursor or the ormation o reactive andselective organozinc reagents under salt-ree conditions. Historically,the diiculty in preparing organozinc reagents that has preventedtheir widespread use is due to their highly pyrophoric nature as wellas the generation o byproducts. The use o additives, which removethese byproducts, presents other limitations. Thereore, a method tocontrol the solubility o the byproducts so that they can be removedby simple iltration or centriugation has been developed, and relieson the use o Zn(OMe)
2
as a precursor to the organozinc reagent tobe ormed in solution. Following ormation o the active organozinccompound, iltration or centriugation is ollowed by the desired organictransormation. Examples o such a transormation include the catalyticenantioselective addition o organozincs to imines, conjugate addition,addition to aldehydes (example below), and addition to
b
-nitrostyrene.
HOROHZn(OMe)
2
RMgCl(2 equiv)(3.95 equiv)Et
2
O
Centrifugation 
(–)-MIB (2 mol %)toluene, 0
°
C, 12 h
702684R = Et,
93%, 98% ee
R =
-C
10
H
21
, 63%, 97% ee
Cote, A.; Charette, A. B.
 J. Am. Chem. Soc.
 
2008
,
130
, 2771.
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Reagent for the PMB-protection of Alcohols
Protection with the
 para
-methoxybenzyl protecting group (PMB) has beenan ongoing challenge in organic chemistry due to the limitations withregard to the reagents that can be used. Common reagents typically requireacidic or basic reaction media and present problems that relate to theirlong-term storage. The lepidine ether below (2-(4-methoxybenzyloxy)-4-methylquinoline) was developed to address some o these limitations and,in combination with MeOT, aords an active reagent
in situ
. A plethora oalcohols are readily protected under neutral reaction conditions. Additionally,2-(4-methoxybenzyloxy)-4-methylquinoline is stable, and byproductsgenerated by its use are easily removed through aqueous workup orchromatography.
NMeOMeOPhOHSiMe
3
(2.0 equiv)MeOTf (2.0 equiv)MgO (2.0 equiv)PhCF
3
, rtPhOPMBSiMe
3
701440
80%
Nwoye, E. O.; Dudley, G. B.
Chem. Commun.
 
2007
, 1436.
 
2-(4-Methoxybenzyloxy)-4-methylquinoline701440
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Reagent for Selective Methylhydrazine Addition
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NNNNHNBocMeEtOH,
H
2
NNMeBocNNNCl
699101
CO
2
EtCO
2
EtNNHNOCO
2
Et43% (2 steps)
Kelly, T. R. et al.
J. Am Chem. Soc.
2006
,
128
, 5646.
 
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 Aldrich Is Pleased to Offer Cutting-Edge Tools for Organic Synthesis
 
57
   V   O   L .   4   1 ,   N   O .   3  •   2   0   0   8
Aldrich Chemical Co., Inc.Sigma-Aldrich Corporation
6000 N. Teutonia Ave.Milwaukee, WI 53209, USA
To Place Orders
Telephone 800-325-3010 (USA)FAX 800-325-5052 (USA)or 414-438-2199Mail P.O. Box 2060Milwaukee, WI 53201, USA
Customer & Technical Services
Customer Inquiries 800-325-3010Technical Service 800-231-8327SAFC
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800-244-1173Custom Synthesis 800-244-1173Flavors & Fragrances 800-227-4563International 414-438-385024-Hour Emergency 414-438-3850Web Site sigma-aldrich.comEmailaldrich@sial.com
General Correspondence
Editor 
:
Sharbil J. Firsan, Ph.D.P.O. Box 355, Milwaukee, WI 53201, USA
Subscriptions
To request your
FREE
subscription to the
 Aldrichimica Acta
, please contact us by:Phone:
800-325-3010
(USA)Mail:
Attn: MailroomAldrich Chemical Co., Inc.Sigma-Aldrich CorporationP.O. Box 355Milwaukee, WI 53201-9358
Email:
International customers, please contact your localSigma-Aldrich ofce. For worldwide contact inor-mation, please see the inside back cover.The
 Aldrichimica Acta
is also available on theInternet at
sigma-aldrich.com/acta
.Aldrich brand products are sold through Sigma-Aldrich, Inc. Sigma-Aldrich, Inc., warrants that itsproducts conorm to the inormation contained inthis and other Sigma-Aldrich publications. Purchasermust determine the suitability o the product or itsparticular use. See reverse side o invoice or packingslip or additional terms and conditions o sale.All prices listed in this publication are subject tochange without notice.
 Aldrichimica Acta
(ISSN 0002–5100) is a publicationo Aldrich. Aldrich is a member o the Sigma-AldrichGroup. © 2008 Sigma-Aldrich Co.
VOL. 41, NO. 3 • 2008
“PLEASE BOTHER US.”
Proessor Michael Krische rom the University o Texasat Austin kindly suggested that we make Ir and Rh BARF(BARF = {3,5-(CF
3
)
2
C
6
H
3
}
4
B
) salts. These compoundswith loosely coordinating properties catalyze varioustransormations, including hydrogenation and reductivecoupling, that otherwise do not proceed eectively.
(1) Ngai, M.-Y.; Barchuk, A.; Krische, M. J.
 J. Am. Chem. Soc.
 
2007
,
129
, 280. (2) Ngai, M.-Y.; Kong, J.-R.; Krische, M. J.
J. Org. Chem.
2007
,
72
, 1063.
4Bis(cyclooctadiene)iridium(I) tetrakis(3,5-bis(trifuoromethyl)phenyl)borate
500 mg$116.002 g435.00
3Bis(1,5-cyclooctadiene)rhodium(I)tetrakis[bis(3,5-triluoromethyl)phenyl]borate
100 mg$45.90500 mg183.00
Naturally, we made these useul reagents. It was no bother at all, just a pleasure to beable to help.
Do you have a compound that you wish Aldrich could list, and that would help you in your research by saving you time and money? If so, please send us your suggestion; we will be de-lighted to give it careful consideration. You can contact us in any one of the ways shown on this page and on the inside back cover.
TABLE OF CONTENTS
Transition-Metal-Catalyzed Cross-Couplings Going Green: in
Water 
at RoomTemperature
.............................................................................................................................................................................................................................................
59
Bruce H. Lipshutz 
*
and Subir Ghorai,
University o Caliornia, Santa Barbara
Preparation o Chiral Diamines by the Diaza-Cope Rearrangement (DCR)
.............................................
77
Hyunwoo Kim, Soon Mog So, and Jik Chin,
*
 
University o Toronto
 ; B. Moon Kim,
*
 
Seoul National University
ABOUT OUR COVER
Looking at
The Bridge at Argenteuil 
 (oil on canvas, 60
×
79.7 cm) rom adistance o ten eet or so, ClaudeMonet’s brushstrokes blend to yield aconvincing view o the river Seine andthe pleasure boats that drew touriststo Argenteuil. Up close, however, eachdab o paint is distinct, and the scenedissolves into a mosaic o paint—brilliant, unblended tones o blue,red, green, and yellow. In the water,quick, luid skips o the brush mimicthe lapping surace. In the trees, thickerpaint is applied with denser, stubbierstrokes. The igure in the sailboat isonly a ghostly wash o dusty blue, and the women rowing nearby are indicated by mereshorthand.In the early years o impressionism, Monet, Renoir, and others strove to capture theleeting eects o light and atmosphere on the landscape and to transcribe directly andquickly their sensory experience o it. Monet advised his students, “When you go out topaint, try to orget what objects you have beore you, a tree, a house, a ield or whatever.Merely think here is a little square o blue, here an oblong o pink, here a streak o yellow,and paint it just as it looks to you, the exact color and shape, until it gives your own naiveimpression o the scene beore you.”In this early work (1874), Monet (1840–1926) captures a warm, sunny, idyllic day—amoti he used oten and or which he became amous. Today, Monet’s characteristic styleand distinctive brushstroke are still resh, recognizable, and most popular.
This painting is part o the Collection o Mr. and Mrs. Paul Mellon at the NationalGallery o Art, Washington, DC.
Joe Porwoll, PresidentAldrich Chemical Co., Inc.
Photograph © Board o Trustees, National Gallery o Art, Washington.
MBF
3
CCF
3
CF
3
CF
3
CF
3
F
3
CF
3
CF
3
C
M = Ir, Rh

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