4624 Chem. Commun., 2011, 47, 4624–4639 This journal is c The Royal Society of Chemistry 2011 Cite this: Chem. Commun., 2011, 47, 4624–4639 Quaternary centres bearing nitrogen (a-tertiary amines) as products of molecular rearrangements Jonathan Clayden,* Morgan Donnard, Julien Lefranc and Daniel J. Tetlow Received 4th January 2011, Accepted 1st February 2011 DOI: 10.1039/c1cc00049g Quaternary centres bearing a nitrogen substituent (a-tertiary amines and their derivatives) are found in a variety of bioactive molecules but pose a major challenge in synthesis, particularly when enantiomeric purity is required. Approaches comparable to those used for tertiary alcohols are typically hampered by the poor electrophilicity of imines, requiring powerful nucleophiles that may also act as bases. A set of powerful alternative approaches make use of the rearrangement of readily available precursors, often (but not always) with formation of a new tertiary carbon to nitrogen bond. In this Feature Article we review the scope, limitations and specificities of some of these rearrangements in order to illuminate their synthetic potential. 1. Introduction Among the simple structural classes which form the building blocks of organic chemistry, a-tertiary amines 1 pose a surprisingly difficult synthetic challenge—especially when the quaternary carbon centre has to be synthesised in an enantio- selective way. Nonetheless, their wide occurrence in naturally occurring and synthetic bioactive molecules 1 (Fig. 1) has provided an impetus for the development of a number of synthetic strategies over the last 50 years. The most common approach has been the addition of a nucleophile to a ketimine, 2 but the lack of reactivity of these species coupled School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom. E-mail: [email protected]Daniel J. Tetlow, Julien Lefranc, Morgan Donnard and Jonathan Clayden Jonathan Clayden was born in Uganda in 1968, grew up in Essex, and was an undergraduate at Churchill College, Cambridge. In 1992 he completed a PhD at the University of Cambridge with Dr Stuart Warren. After postdoctoral work with Prof. Marc Julia at the E ´ cole Normale Supe ´rieure in Paris, he moved in 1994 to Manchester and in 2001 was promoted to a chair in organic chemistry. He has published over 175 papers, and his research interests encompass various areas of synthesis and stereochemistry, particularly where conformation has a role to play: asymmetric synthesis, atropisomerism, organolithium chemistry, dearomatising reactions and remote stereocontrol. He is co-author of the best-selling textbook ‘‘Organic Chemistry’’(OUP, 2001), and of ‘‘Organolithiums: Selectivity for Synthesis’’ (Pergamon, 2002). He has received the Royal Society of Chemistry’s Meldola (1997) and Corday Morgan (2003) medals, Stereochemistry Prize (2005) and Hickinbottom Fellowship (2006). Morgan Donnard was born in 1980 in Strasbourg, France. After a stay in Netherlands at DSM Pharmaceuticals where he worked with Prof. Johannes De Vries, he returned to Strasbourg where he graduated in chemistry and biology in 2005 with Dr Andre ´ Mann. In 2008, he completed his doctoral studies with Prof. Jacques Eustache at the E ´ cole Nationale Supe ´rieure de Chimie in Mulhouse (F). In 2011, after 2 years working as a postdoctoral researcher with Prof. Jonathan Clayden on asymmetric organolithium rearrangements, Morgan joined Dr Nicolas Blanchard in Mulhouse and his research interests are focusing on ynamide reactivity and organo-metallic chemistry. Julien Lefranc was born in 1984 in Marseille, France. He studied chemistry at the Universite ´ de la Me ´diterrane´e, Marseille, and then moved to the E ´ cole Nationale Supe ´rieure de Chimie de Montpellier in 2006. In 2008 He joined the group of Prof. Jonathan Clayden where he is now completing his PhD working on the applications of new carbolithiation reactions. Daniel J. Tetlow was born in Warrington, UK, in 1984. He graduated from the University of Leeds in 2007, after which he undertook a postgraduate research project with Prof. Jonathan Clayden at the University of Manchester. His PhD work focuses on the asymmetric synthesis of hindered amine derivatives. ChemComm Dynamic Article Links www.rsc.org/chemcomm FEATURE ARTICLE Downloaded by University of Oxford on 06 April 2011 Published on 07 March 2011 on http://pubs.rsc.org | doi:10.1039/C1CC00049G View Online
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4624 Chem. Commun., 2011, 47, 4624–4639 This journal is c The Royal Society of Chemistry 2011
Cite this: Chem. Commun., 2011, 47, 4624–4639
Quaternary centres bearing nitrogen (a-tertiary amines) as products
of molecular rearrangements
Jonathan Clayden,* Morgan Donnard, Julien Lefranc and Daniel J. Tetlow
Received 4th January 2011, Accepted 1st February 2011
DOI: 10.1039/c1cc00049g
Quaternary centres bearing a nitrogen substituent (a-tertiary amines and their derivatives) are
found in a variety of bioactive molecules but pose a major challenge in synthesis, particularly
when enantiomeric purity is required. Approaches comparable to those used for tertiary alcohols
are typically hampered by the poor electrophilicity of imines, requiring powerful nucleophiles that
may also act as bases. A set of powerful alternative approaches make use of the rearrangement
of readily available precursors, often (but not always) with formation of a new tertiary carbon to
nitrogen bond. In this Feature Article we review the scope, limitations and specificities of some
of these rearrangements in order to illuminate their synthetic potential.
1. Introduction
Among the simple structural classes which form the building
blocks of organic chemistry, a-tertiary amines 1 pose a
surprisingly difficult synthetic challenge—especially when the
quaternary carbon centre has to be synthesised in an enantio-
selective way. Nonetheless, their wide occurrence in naturally
occurring and synthetic bioactive molecules1 (Fig. 1) has
provided an impetus for the development of a number of
synthetic strategies over the last 50 years. The most common
approach has been the addition of a nucleophile to a
ketimine,2 but the lack of reactivity of these species coupled
School of Chemistry, University of Manchester, Oxford Road,Manchester, M13 9PL, United Kingdom.E-mail: [email protected]
Daniel J. Tetlow, Julien Lefranc, Morgan Donnard and
Jonathan Clayden
Jonathan Clayden was born in Uganda in 1968, grew up in Essex,and was an undergraduate at Churchill College, Cambridge. In1992 he completed a PhD at the University of Cambridge withDr Stuart Warren. After postdoctoral work with Prof. Marc Juliaat the Ecole Normale Superieure in Paris, he moved in 1994 toManchester and in 2001 was promoted to a chair in organicchemistry. He has published over 175 papers, and his researchinterests encompass various areas of synthesis and stereochemistry,particularly where conformation has a role to play: asymmetricsynthesis, atropisomerism, organolithium chemistry, dearomatisingreactions and remote stereocontrol. He is co-author of thebest-selling textbook ‘‘Organic Chemistry’’(OUP, 2001), and of‘‘Organolithiums: Selectivity for Synthesis’’ (Pergamon, 2002).He has received the Royal Society of Chemistry’s Meldola (1997)and Corday Morgan (2003) medals, Stereochemistry Prize (2005)and Hickinbottom Fellowship (2006).
Morgan Donnard was born in 1980 in Strasbourg, France. After a stay in Netherlands at DSMPharmaceuticals where he worked withProf. Johannes De Vries, he returned to Strasbourg where he graduated in chemistry and biology in 2005 with Dr Andre Mann. In 2008,he completed his doctoral studies with Prof. Jacques Eustache at the Ecole Nationale Superieure de Chimie in Mulhouse (F). In 2011,after 2 years working as a postdoctoral researcher with Prof. Jonathan Clayden on asymmetric organolithium rearrangements, Morganjoined Dr Nicolas Blanchard in Mulhouse and his research interests are focusing on ynamide reactivity and organo-metallic chemistry.
Julien Lefranc was born in 1984 in Marseille, France. He studied chemistry at the Universite de la Mediterranee, Marseille, and thenmoved to the Ecole Nationale Superieure de Chimie de Montpellier in 2006. In 2008 He joined the group of Prof. Jonathan Claydenwhere he is now completing his PhD working on the applications of new carbolithiation reactions.
Daniel J. Tetlow was born inWarrington, UK, in 1984. He graduated from the University of Leeds in 2007, after which he undertook apostgraduate research project with Prof. Jonathan Clayden at the University of Manchester. His PhD work focuses on the asymmetricsynthesis of hindered amine derivatives.
4634 Chem. Commun., 2011, 47, 4624–4639 This journal is c The Royal Society of Chemistry 2011
t-butyl ester 136 with solid CsOH in dichloroethane formed
the desired amine 137 in 73% yield and 92% ee. Variation of
the aromatic group of the ammonium salt increased the
selectivity up to 99% ee.
An enantioselective [1,2]-Stevens rearrangement was reported
in 2008 by Tomooka and co-workers,81 with sugar-derived
alkoxides as chiral promoters. The treatment of the ammonium
salt 138 in the presence of a chiral alkoxide led to the forma-
tion of the enantiomerically enriched a-tertiary amine 139
(4–61% ee) (Scheme 43).
Metal-containing ammonium ylids undergo tandem [1,2]-
Stevens-1,2 alkyl migration of (Scheme 44).82 In the presence
of a metal, the alkyne p-complex 144 is generated and the corres-
ponding metal-containing ammonium ylid 146 is formed. 146
undergoes a [1,2]-Stevens rearrangement followed by alkyl
migration to generate the N-fused tricyclic indole 148.
Different metallic complexes were also investigated with only
W(CO)6 providing the desired product. Photoirradiation was
crucial for the generation of the unsaturated tungsten species.
The carbene intermediate was trapped using 10% Et3SiH,
allowing the a-tertiary amine 149 to be recovered in 7% yield
(Scheme 44).
Lewis-acids can be used to promote [1,2]-Stevens rearrange-
ment of proline derivatives.83 with complete C to N to C
chirality transfer (Scheme 45). The desired free amine was
obtained in moderate to good yields via a mechanism involving
the formation of 151 with a high degree of stereospecificity.
Addition of triethylamine promotes the formation of 152
which can recombine after homolysis to form the desired
amine 154 (after hydrolysis) (Scheme 45).
6.2 Sommelet–Hauser rearrangement
In 1937, M. Sommelet observed that the decomposition of the
quaternary ammonium salt 155 led to the formation of the
rearranged amine 156 (Scheme 46).84 In 1957, C. Hauser investi-
gated the rearrangement of the benzyltrimethylammonium ion.85
Scheme 37 Synthesis of oxazolidines using Stevens rearrangement.
Scheme 38 Synthesis of glycine derivatives.
Scheme 39 Synthesis of proline-derivatives using [2,3]-Stevens
rearrangement.
Scheme 40 Amino acids synthesis using metal-carbene to initiate
Stevens rearrangement.
Table 2
Entry X Catalyst Yield (%)
1 H Cu(acac)2 592 H Cu(hfacac)2 483 H Rh2(OAc)4 364 COMe Cu(acac)2 545 COMe Cu(hfacac)2 666 COMe Rh2(OAc)4 377 CO2Et Cu(acac)2 598 CO2Et Cu(hfacac)2 819 CO2Et Rh2(OAc)4 42
Scheme 41
Scheme 42 Stevens rearrangement under heterogeneous conditions.Dow
This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 4624–4639 4637
gives better results in terms of yield and er, while the E
isomer reacts poorly to give the desired product in a racemic
mixture.
Attempts to rearrange more hindered analogues of benzylic
substrates 166 give poor yields of the desired product. Alter-
native ways of generating the required benzylic organolithium
were investigated with the aim of circumventing this problem.
The solution emerged during work on the deprotonation
of N-vinyl ureas. While investigating deprotonation with bases
more nucleophilic than LDA and lithium amide derivatives,
we discovered that the attack of an alkyllithium on vinyl urea
179 gave not the expected allyl lithium by deprotonation
but instead a carbolithiated intermediate 180 by nucleophilic
attack on the vinyl group. Addition of DMPU to promote
rearrangement gives the a-tertiary amine derivative 181 in
very good yields (up to 86%) (Scheme 51).100 The carbolithia-
tion is remarkable for its ‘‘umpolung’’ character, with attack
occurring on the more nucleophilic carbon of the enamine
derivative 179. The carbolithiation is also diastereospecific:
substrates 179 with E or Z CQC double bonds101 give
different diastereoisomers of the product 180. X-ray structures
of the products 181 allowed us to conclude (assuming
a retentive rearrangement93) that the carbolithiation is a syn
addition. A wide range of alkyllithiums and aromatic urea
substituents are tolerated, making this approach particularly
versatile for the synthesis of derivatives of branched a-tertiaryamines (Scheme 51). Encouraging preliminary results on an
enantioselective version of this tandem reaction are currently
in progress.
7.2 Nitrogen to carbon carboxyl migration
In 2007, Coudert et al. reported a tandem carbolithiation
and N-to-C acyl migration of vinyl carbamates 182 to give
a-quaternary a-amino esters 184 (Scheme 52).102 The general
behaviour of the carbolithiation step is similar to the one
observed with vinyl ureas (section 7.1).100 However the carbamate
carbolithiation seems more tolerant to different substrates
and was extended to a wider range of organolithium reagents.
Even lithium amides and lithium phosphides added to
the CQC double bond in satisfactory to excellent yields
(up to 95%)102,103 (Scheme 52) allowing the synthesis of
unusual a-amino acid precursors. No details are reported of
an enantioselective version of this reaction.
8. Conclusions
The range of reactivity embodied in rearrangement reactions
means that many classes of a-tertiary amines may be made
using rearrangement strategies. New reactions, such as the
rearrangement of aryl ureas, and those based on carbolithiation
chemistry, are still emerging, and many of the rearrangements
described in this review still do not exist in asymmetric form.
Concepts explored in this field will also be of value in the
synthesis of other challenging targets—quaternary centres adjacent
to sulfur for example.104
Acknowledgements
We are grateful to the EPSRC for research grants, and to
AstraZeneca for support.
Notes and references
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