University of Strathclyde
Cite this: DOI: 10.1039/x0xx00000xReceived 00th January 2012,Accepted 00th January 2012DOI: 10.1039/x0xx00000xDehydromethylation of utility amide 2,2,6,6tetramethylpiperidide (TMP) to aza-allyl 2,2,6-trimethyl-1,2,3,4-tetrahydropyridide (TTHP): synthesis of a homologous series of alkali metal (Li, Na, K) TTHP compounds?Alan R. Kennedy,a Sarah M. Leenhouts,a John J. Liggat,a Antonio J. Martínez-Martínez,a Kimberley Miller,a Robert E. Mulvey,*a Charles T. O’Hara,*a Philip O’Keefe,b and Alan StevenbA general thermolysis reaction for the transformation of Group 1 TMP compounds (LiTMP, NaTMP, KTMP) to 1-aza-allylic TTHP derivatives is reported. TMEDA accelerates the reaction and produces the crystalline complexes [(TMEDA)LiTTHP] and [(TMEDANaTTHP)2]. Methane elimination during the transformational process was confirmed via TVA coupled to MS.Lithium TMP (TMP=2,2,6,6-tetramethylpiperidide) was introduced inconspicuously in 1972 listed among tables of lithium alkylamides comparing its performance as a non-nucleophilic base for ring opening cyclohexene oxide and for generating boron stabilised -carbanions.PEVuZE5vdGU+PENpdGU+PEF1dGhvcj5LaXNzZWw8L0F1dGhvcj48WWVhcj4xOTcyPC9ZZWFyPjxS
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ADDIN EN.CITE.DATA 1 Forty years on LiTMP is a leading utility amide,PEVuZE5vdGU+PENpdGU+PEF1dGhvcj5NdWx2ZXk8L0F1dGhvcj48WWVhcj4yMDEzPC9ZZWFyPjxS
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Pn==
ADDIN EN.CITE.DATA 3 Much of the success of the TMP anion as a proton abstractor lies in its special architecture. Four electron donating methyl substituents simultaneously sterically shield and electronically enhance the adjacent anionic nitrogen, that heads a stable, cyclic framework that cannot undergo -hydride elimination. Exploiting these attributes, a new generation of metallating agents has recently been developed using TMP as the Br?nsted base engine within bimetallic organometallic-amidometallic or amidometallic-salt formulations. Lithium is often the mediator within these bimetallic bases enabling a nominally less reactive metal [e.g., Zn in “tBu2ZnLiTMP”; ADDIN EN.CITE <EndNote><Cite><Author>Kondo</Author><Year>1999</Year><RecNum>1215</RecNum><DisplayText><style face="superscript">4</style></DisplayText><record><rec-number>1215</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398776507">1215</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Kondo, Yoshinori</author><author>Shilai, Manabu</author><author>Uchiyama, Masanobu</author><author>Sakamoto, Takao</author></authors></contributors><titles><title>TMP?Zincate as Highly Chemoselective Base for Directed Ortho Metalation</title><secondary-title>J. Am. Chem. Soc.</secondary-title></titles><periodical><full-title>J. Am. Chem. Soc.</full-title></periodical><pages>3539-3540</pages><volume>121</volume><number>14</number><dates><year>1999</year><pub-dates><date>1999/04/01</date></pub-dates></dates><publisher>American Chemical Society</publisher><isbn>0002-7863</isbn><urls><related-urls><url> Mg in “(TMP)MgClLiCl”PEVuZE5vdGU+PENpdGU+PEF1dGhvcj5LcmFzb3Zza2l5PC9BdXRob3I+PFllYXI+MjAwNjwvWWVh
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ADDIN EN.CITE.DATA 5] to perform the TMP-executed deprotonation. To our knowledge no previous study has deliberately attempted to modify the special architecture of TMP starting from TMP itself. ADDIN EN.CITE <EndNote><Cite><Author>Martinez-Martinez</Author><Year>2014</Year><RecNum>1210</RecNum><DisplayText><style face="superscript">6</style></DisplayText><record><rec-number>1210</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398774300">1210</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Martínez-Martínez, A. J.</author><author>Armstrong, D. R.</author><author>Conway, B.</author><author>Fleming, B. J.</author><author>Klett, J.</author><author>Kennedy, A. R.</author><author>Mulvey, R. E.</author><author>Robertson, S. D.</author><author>O'Hara, C. T.</author></authors></contributors><titles><title>Pre-inverse-crowns: synthetic, structural and reactivity studies of alkali metal magnesiates primed for inverse crown formation</title><secondary-title>Chem. Sci.</secondary-title></titles><periodical><full-title>Chem. Sci.</full-title></periodical><pages>771-781</pages><volume>5</volume><number>2</number><dates><year>2014</year></dates><publisher>The Royal Society of Chemistry</publisher><isbn>2041-6520</isbn><work-type>10.1039/C3SC52816B</work-type><urls><related-urls><url> Since even subtle modifications could have profound effects on reactivity we have pursued this goal in the present study. Hints that direct TMP modification should be realisable are found in mass spectrometric (70 eV) studies of (TMP)2Al(X) (where X = Me, nBu, Ph, tBuS) through observation of loss of Me(TMP) fragments ADDIN EN.CITE <EndNote><Cite><Author>Krossing</Author><Year>1997</Year><RecNum>1214</RecNum><DisplayText><style face="superscript">7</style></DisplayText><record><rec-number>1214</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398775796">1214</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Krossing, Ingo</author><author>N?th, Heinrich</author><author>Tacke, Christiane</author><author>Schmidt, Martin</author><author>Schwenk, Holger</author></authors></contributors><titles><title>Synthesis and Structures of Bis(tetramethylipiperidino)aluminum Halides-X-ray Crystal Structures of tmp2AlX (X = Cl, Br, I) and [tmp2A1(μ-F)l2</title><secondary-title>Chem. Ber.</secondary-title></titles><periodical><full-title>Chem. Ber.</full-title></periodical><pages>1047-1052</pages><volume>130</volume><number>8</number><keywords><keyword>Bis(tetramethylipiperidino)aluminum halides</keyword><keyword>Alkoxy((tetramethylpiperidino)aluminum halides</keyword><keyword>27Al-NMR spectra</keyword><keyword>Aluminum</keyword><keyword>Amides</keyword><keyword>Synthetic methods</keyword><keyword>Bridging ligands</keyword></keywords><dates><year>1997</year></dates><publisher>WILEY-VCH Verlag</publisher><isbn>1099-0682</isbn><urls><related-urls><url> and in the characterisation of an osmium imine complex, ADDIN EN.CITE <EndNote><Cite><Author>Yandulov</Author><Year>2002</Year><RecNum>1213</RecNum><DisplayText><style face="superscript">8</style></DisplayText><record><rec-number>1213</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398775403">1213</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Yandulov, Dmitry V.</author><author>Huffman, John C.</author><author>Caulton, Kenneth G.</author></authors></contributors><titles><title>Conventional Lithium Bases as Unconventional Sources of Methyl Anion:? Facile Me?Si and Me?C Bond Cleavage in RLi, R2NLi, and BR4- by an Electrophilic Osmium Dihydride</title><secondary-title>Organometallics</secondary-title></titles><periodical><full-title>Organometallics</full-title></periodical><pages>4030-4049</pages><volume>21</volume><number>20</number><dates><year>2002</year><pub-dates><date>2002/09/01</date></pub-dates></dates><publisher>American Chemical Society</publisher><isbn>0276-7333</isbn><urls><related-urls><url> the imino ligand of which derives from LiTMP where TMP has lost one Me arm completely and has another partially severed through deprotonation. Here we report the remarkably straightforward conversion of the TMP skeleton to a 1-aza-allylic modification manifested in a novel isolable homologous series of alkali metal complexes. Conversion occurs via methane elimination as established through Thermal Volatilisation Analysis (TVA), with elimination becoming easier progressively for “M” in MTMP in the sequence H<Li<Na<K.Scheme 1. Thermolysis of MTMP to MTTHP. a Conversion by NMR. b Isolated yield, quantitative conversion by NMR.Accessed through thermolysis in refluxing methylcyclohexane solution, conversion of the alkali metal TMP compound to a TTHP (2,2,6-trimethyl-1,2,3,4-tetrahydropyridide) derivative was demonstrated in five new compounds of empirical formula [(TMEDA)xM(TTHP)] where M=Li, x=0, 1; M=Li, x=1, 1TMEDA; M=Na, x=0, 2; M=Na, x=1, 2TMEDA and M=K, x=0, 3 (TMEDA=N,N,N,N-tetramethylethylenediamine) (Scheme 1). Two important trends emerge from the synthetic data. TMEDA, a bidentate chelating amine, exerts an activating effect. The lithium case for example shows an increase in the TMP to TTHP conversion from 25% to 100% on adding TMEDA. Reflux times for comparable yields of TTHP products are also significantly reduced by TMEDA intervention. A group trend is also evident with increasing conversion rates on increasing the size of the alkali metal. In the extreme case [Li(TTHP)], 1, is only accessible in a 25% (in situ NMR studies) yield following an 18 hour reflux reaction; whereas potassium congener [K(TTHP)] 3 can be obtained in an isolated crystalline yield of 83% (quantitative by NMR data) after heating the reaction solution to reflux for only 3 h. Continuing this trend, when M is H in TMP(H) a 24 h reflux reaction failed to produce any conversion at all indicating that an alkali metal is essential for the thermally induced TMP dehydromethylation. Interestingly, however, TMP(H) can undergo loss of one Me arm under the greater power of electron impact ionisation (EI) during a GCMS study as evidenced by a peak at 126.22 corresponding to a [TMP-Me-1e?]+ fragment with no peak observed for the unstable molecular ion [TMP-1e?]+.3314700-788035Figure 2. Molecular structure of 2TMEDA. Hydrogen atoms omitted for simplicity with exception of the olefinic hydrogen on C2. Thermal ellipsoids are displayed at 35% probability. The symmetry operation to generate the equivalent atoms labelled with ’ is -x,-y,-z+2.00Figure 2. Molecular structure of 2TMEDA. Hydrogen atoms omitted for simplicity with exception of the olefinic hydrogen on C2. Thermal ellipsoids are displayed at 35% probability. The symmetry operation to generate the equivalent atoms labelled with ’ is -x,-y,-z+2.All five new compounds have been characterised by 1H and 13C (and also 7Li for 1 and 1TMEDA) NMR spectroscopy in d8-THF solution (see ESI). Their common aza-allylic character is implicated by the unsaturated NC(CH3)=C(H) unit within their TTHP rings with CH3 resonances located at 1.57, 1.55, 1.58, 1.56 and 1.55 ppm and those for -C(H) at 3.37, 3.31, 3.27, 3.23 and 3.14 ppm for 1, 1TMEDA, 2, 2TMEDA and 3 respectively. Four of the five new compounds capable of isolation in a pure solid form (the exception being 1) were further characterised by diffusion-ordered NMR spectroscopy (DOSY). 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ADDIN EN.CITE.DATA 9 DOSY experiments can be employed to distinguish distinct components of solution mixtures and to estimate their sizes, which are inversely proportional to their diffusion coefficients (D). Measured against internal references of known molecular weight, D values were obtained from solution concentrations of 40 mgmL-1 enabling size estimation. Recently this method was used to distinguish between tetrameric and trimeric polymorphs of LiTMP. ADDIN EN.CITE <EndNote><Cite><Author>Hevia</Author><Year>2013</Year><RecNum>1219</RecNum><DisplayText><style face="superscript">10</style></DisplayText><record><rec-number>1219</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398779037">1219</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Hevia, Eva</author><author>Kennedy, Alan R.</author><author>Mulvey, Robert E.</author><author>Ramsay, Donna L.</author><author>Robertson, Stuart D.</author></authors></contributors><titles><title>Concealed Cyclotrimeric Polymorph of Lithium 2,2,6,6-Tetramethylpiperidide Unconcealed: X-Ray Crystallographic and NMR Spectroscopic Studies</title><secondary-title>Chem. Eur. J.</secondary-title></titles><periodical><full-title>Chem. Eur. J.</full-title></periodical><pages>14069-14075</pages><volume>19</volume><number>42</number><keywords><keyword>amides</keyword><keyword>crystal structures</keyword><keyword>lithium</keyword><keyword>NMR spectroscopy</keyword><keyword>polymorphism</keyword></keywords><dates><year>2013</year></dates><publisher>WILEY-VCH Verlag</publisher><isbn>1521-3765</isbn><urls><related-urls><url> Summarising our DOSY results (see ESI), the aggregation states of 1TMEDA and 2TMEDA seen in the crystal (see below) appear retained in d8-THF solution though with TMEDA substituted by the stronger monodentate donor in [(d8-THF)2LiTTHP] and [(d8-THFNaTTHP)2] respectively. However, a monosolvated dimeric variant, [d8-THF(LiTTHP)2] cannot be ruled out in the former case. Mimicking its sodium congener, KTTHP 3 appears to exist as a bi-solvated dimer [(d8-THFKTTHP)2] in this polar medium.X-ray crystallographic characterisation of 1TMEDA and 2TMEDA revealed monomeric (Fig. 1) and dimeric (Fig. 2) structures respectively. Thus the former departs from the open dimer structure of its TMP counterpart [(TMEDA)Li(TMP)Li(TMP)] [note the exact analogy (TMEDA)LiTMP is unknown in the solid though it exists in solutionPEVuZE5vdGU+PENpdGU+PEF1dGhvcj5XaWxsaWFyZDwvQXV0aG9yPjxZZWFyPjE5OTM8L1llYXI+
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ADDIN EN.CITE.DATA 12 anion, derived from LiTMP and NaTMP respectively by loss of one Me and one adjacent -H atom (implying MeH elimination) to create a C=C double bond locked within the NC5 ring. TTHP anions in both have comparable, and due to the imposed unsaturation, asymmetrical dimensions. Bond lengths in the contracted side [N1-C1-C2, 1.363(2)/1.357(3) ? in 1TMEDA; 1.356(2)/1.370(3)? in 2TMEDA; cf., the opposite side N1-C5-C4, 1.469(2)/1.533(2)? in 1TMEDA; N1-C6-C5, 1.475(2)/1.536(3)? in 2TMEDA, see ESI] are consistent with a delocalised NCN electronic distribution. In keeping with sp2 hybridisation, carbon atoms C1 and C2 occupy distorted trigonal planar environments, meaning that the new anion has lost the chair conformation of TMP with pronounced ring puckering at bis-Me-substituted C5. All other structural parameters appear unremarkable. Aza-allylic ligands often bind 3 to alkali metals ADDIN EN.CITE <EndNote><Cite><Author>Caro</Author><Year>2001</Year><RecNum>1224</RecNum><DisplayText><style face="superscript">12b</style></DisplayText><record><rec-number>1224</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398851365">1224</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Caro, Catherine F.</author><author>Lappert, Michael F.</author><author>Merle, Philippe G.</author></authors></contributors><titles><title>Review of metal 1-azaallyl complexes</title><secondary-title>Coord. Chem. Rev.</secondary-title></titles><periodical><full-title>Coord. Chem. Rev.</full-title></periodical><pages>605-663</pages><volume>219–221</volume><number>0</number><keywords><keyword>Metal 1-azaallyl complexes</keyword><keyword>Bonding modes</keyword><keyword>Four-membered metalloacycles</keyword></keywords><dates><year>2001</year><pub-dates><date>10//</date></pub-dates></dates><isbn>0010-8545</isbn><urls><related-urls><url>(01)00361-7</electronic-resource-num></record></Cite></EndNote>12b in contrast to the 1 mode displayed in both 1TMEDA and 2TMEDA. Consequently the M-N(TTHP) bond lengths are typical of comparable M-amido bonds such as the terminal M-TMP bond in [(TMEDA)Li(TMP)Li(TMP)] [1.883(4) cf., 1.885(5)?] and the bridging M-TMP bond in [(TMEDANaTMP)2] [mean 2.459 cf., 2.470?]. TMEDA chelation completes the M bonding in 1TMEDA and 2TMEDA rendering Li three coordinate and Na four coordinate .While TMEDA-chelated Na dimers are well known [e.g., in (TMEDANaNiPr2)2], congeneric Li monomers are comparatively rare. ADDIN EN.CITE <EndNote><Cite><Author>Mulvey</Author><Year>2013</Year><RecNum>1209</RecNum><DisplayText><style face="superscript">2a</style></DisplayText><record><rec-number>1209</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1398773096">1209</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Mulvey, Robert E.</author><author>Robertson, Stuart D.</author></authors></contributors><titles><title>Synthetically Important Alkali-Metal Utility Amides: Lithium, Sodium, and Potassium Hexamethyldisilazides, Diisopropylamides, and Tetramethylpiperidides</title><secondary-title>Angew. Chem. Int. Ed.</secondary-title></titles><periodical><full-title>Angew. Chem. Int. Ed.</full-title><abbr-1>Angew. Chem., Int. Ed.</abbr-1></periodical><pages>11470-11487</pages><volume>52</volume><number>44</number><keywords><keyword>alkali metals</keyword><keyword>heterometallic compounds</keyword><keyword>molecular structure</keyword><keyword>secondary amide</keyword><keyword>solution state</keyword></keywords><dates><year>2013</year></dates><publisher>WILEY-VCH Verlag</publisher><isbn>1521-3773</isbn><urls><related-urls><url> To force monomerisation a TMEDA-complexed Li must be partnered by an anion of sufficient steric stature. TMP with its greater steric bulk would therefore seem the better prospect for effecting monomerisation, yet [(TMEDA)Li(TMP)Li(TMP)] is dinuclear whereas 1TMEDA is mononuclear. Hemisolvation versus full solvation is clearly a key factor here since in solution [(TMEDALi(TMP)Li(TMP)] is known to disassemble to a mixture of unsolvated, higher aggregated LiTMP and mononuclear [(TMEDA)LiTMP], though in excess TMEDA the latter forms exclusively.-33115253395980Figure 1. Molecular structure of 1TMEDA. Hydrogen atoms omitted for clarity with exception of the olefinic hydrogen on C2. Thermal ellipsoids are displayed at 30% probability.00Figure 1. Molecular structure of 1TMEDA. Hydrogen atoms omitted for clarity with exception of the olefinic hydrogen on C2. Thermal ellipsoids are displayed at 30% probability.Suspected methane elimination leading to TTHP formation was confirmed for all MTMP (M=Li, Na, K) complexes via TVA performed under high vacuum, coupled to MS. Full product scans (see ESI) show LiTMP evolves gas in two distinct steps, Tpeak 131 and 197?C, with considerable production of non-condensable products associated with the second step. NaTMP behaves similarly but with the higher temperature process more dominant and moving to lower temperature (163?C, see Fig. 3). For KTMP there is only a single gas evolution process, dominated by non-condensable gases (100?C). 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AG==
ADDIN EN.CITE.DATA 12d, 12e, 13 with, as here, gas elimination most favoured by larger alkali metals and by adding donor ligands, though these systems are stabilised by the presence of aryl groups in contrast to our fully aliphatic systems. Elimination of “LiMe” from LiTMP and a subsequent Me? executed deprotonation has also been implicated in forming the aforementioned osmium complex, though the deprotonation occurs at a lateral Me site to generate an imidoalkyl isomer of the enamido TTHP anion. Significantly our TVA studies of MTMP compounds did not detect any ethane (only traces of ethene from a secondary decomposition process, see ESI), thus decreasing the likelihood of an alternative mechanism involving Me radicals not anions. Significantly no Me deprotonation (to CH2) was seen here in contrast to that observed in a potassium aluminate bis-TMP system ADDIN EN.CITE <EndNote><Cite><Author>Conway</Author><Year>2010</Year><RecNum>1229</RecNum><DisplayText><style face="superscript">14</style></DisplayText><record><rec-number>1229</rec-number><foreign-keys><key app="EN" db-id="fvaetrd939wts9e52agv9sx2xwrpz2epv5s9" timestamp="1400168734">1229</key></foreign-keys><ref-type name="Journal Article">17</ref-type><contributors><authors><author>Conway, Ben</author><author>Kennedy, Alan?R</author><author>Mulvey, Robert?E</author><author>Robertson, Stuart?D</author><author>?lvarez, Joaquin García</author></authors></contributors><titles><title>Structurally Stimulated Deprotonation/Alumination of the TMP Anion</title><secondary-title>Angew. Chem. Int. Ed.</secondary-title></titles><periodical><full-title>Angew. Chem. Int. Ed.</full-title><abbr-1>Angew. Chem., Int. Ed.</abbr-1></periodical><pages>3182-3184</pages><volume>49</volume><number>18</number><keywords><keyword>alkali metals</keyword><keyword>aluminum</keyword><keyword>amides</keyword><keyword>metalation</keyword><keyword>steric effects</keyword></keywords><dates><year>2010</year></dates><publisher>WILEY-VCH Verlag</publisher><isbn>1521-3773</isbn><urls><related-urls><url> nor was any metallation of TMEDA observed.15 Scheme 2. Possible mechanism for the MTMPMTTHP transformation [M=Li (1, 1TMEDA), Na (2, 2TMEDA), K (3)].ConclusionsA simple thermally induced transformation of synthetically important alkali metal TMP compounds to TTHP derivatives has been established. Such decompositions could explain why LiTMP can sometimes give poor yields in reactions performed at elevated temperatures in hydrocarbon solvents.16 The fact that most TTHP compounds can be made in high yield and high purity bodes well for future studies screening their reactivity.Notes and referencesa WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK. E-mail: r.e.mulvey@strath.ac.uk; charlie.ohara@strath.ac.uk.b Chemical Development, AstraZeneca, Silk Road Business Park, Charter Way, Macclesfield, SK10 2NA, UK.? Electronic Supplementary Information (ESI) available: Experimental procedures, full characterization, TVA, data and copies of 1H, 7Li and 13C NMR spectra. XRD crystallographic data, CCDC [1002045-1002046]. See DOI: 10.1039/c000000x/25400-6099175Figure 3. Overlay TVA thermogram of the methane evolution curves for MTMP (M=Li, Na and K).00Figure 3. Overlay TVA thermogram of the methane evolution curves for MTMP (M=Li, Na and K).We gratefully acknowledge financial support from AstraZeneca and the University of Strathclyde (studentship to S.M.L.), the Royal Society (Wolfson research merit award to R.E.M.) and the EPSRC (Career Acceleration Fellowship, EP/J001872/1 to C.T.O.H.; EP/K001183/1 to R.E.M). Prof. Hevia is also thanked for insightful discussions. ADDIN EN.REFLIST 1 (a) C. L. Kissel and B. Rickborn, J. Org. Chem., 1972, 37, 2060-2063; (b) M. W. Rathke and R. Kow, J. Am. Chem. Soc., 1972, 94, 6854-6856.2 (a) R. E. Mulvey and S. D. Robertson, Angew. Chem., Int. Ed., 2013, 52, 11470-11487; (b) A. Harrison-Marchand and F. Mongin, Chem. Rev., 2013, 113, 7470-7562; (c) F. Mongin and A. Harrison-Marchand, Chem. Rev., 2013, 113, 7563-7727.3 (a) C. A. Lenz and M. Rychlik, Tetrahedron Lett., 2013, 54, 883-886; (b) D. M. Hodgson and R. S. D. Persaud, Beilstein J. Org. Chem., 2012, 8, 1896-1900; (c) J. Michaux, B. Bessières and J. 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