Talk:Todd:Catalytic, Asymmetric Pictet-Spengler Reaction

Use this page for discussion. Preface questions/comments with initials. Reply to questions but don't delete the question. If things are resolved, move them to the "resolved" section at the bottom of the page.

General Things that Need Doing

1. Papers below need looking at - whether to include or not
2. More papers should be found, either by doing citation searches on papers already included, or doing new searches.
3. Papers that are already in the review, and have been summarized, need checking (see Quality Control, below)
4. Easy thing - papers below need DOI links inserting so they may be found easily, formatted like this example: Stoeckigt and Waldmann Angew 2011

Some specific things that currently need doing:
1. General description of what the PS reaction is, with a scheme of the very first example - essentially a description of the very first paper.
2. Examples of important bioactive molecules that can be made with the PS need to be found.
3. The Lewis Acid section needs thought. Are there examples of catalytic Lewis Acids?

Please don't use email if at all possible. Use this page or some other public forum. Remember if you want to contribute you are going to need an account on OWW and one on Mendeley where we are collecting citations. There is a shared Dropbox folder for access to all Chemdraw files and PDFs - for access contact Murray

General Comments, either on science or the review more broadly

Suggestions can go directly here or on the main page in italics. Minor comments can go in the sandbox area below.

MHT - Jan19 - the page is quite long. We could consider splitting into sections if anyone is having a browser problem, but otherwise we keep as-is. Much more convenient having everything on one page.

MHT - Jan 21 - In the 2007 Hiemstra work, why does the sulfenyl help? Paper says should stabilize intermediate iminium ion and favour cyclization over competitive enamine formation) Paper gives: The use of N-sulfenyl substituents as protecting groups is known in peptide synthesis; see a) L. Zervas, D. Borovas, E. Gazis, J. Am. Chem. Soc. 1963, 85, 3660 – 3666 ; for reviews on sulfenamide chemistry, see b) F. A. Davis, U. K. Nadir, Org. Prep. Proced. Int. 1979, 11, 33–51; c)L. Craine, M. Raban, Chem. Rev. 1989, 89, 689 – 712 ; d) I. V. Koval, Russ. Chem. Rev. 1996, 65, 452 – 473.

MHT - Jan 22 - This paper is listed in the references, but has it been read and digested, to extract a) relevant info about the PS, but mainly b) mechanistic ideas of relevance? If not, leave the ref where it is, but add note in mech section about the need to include it there. Small-Molecule H-Bond Donors in Asymmetric Catalysis, A. G. Doyle and E. N. Jacobsen, Chem. Rev. 2007, 107, 5713-5743.

MHT - Feb 2 - We will eventually number molecules in all schemes.

MAT - Feb 11 - Added some lines to the "Future Directions" section. Can flesh these out, please comment on relevance.

Sandbox area for minor/temporary comments

This is the place to chat. Use initials for your comments/questions. Inactive chats/resolved things can be cut from here and pasted at the bottom of the page.

KAB - Jan22 - Added two .cdx files to DropBox under "All BINAP-derived" and "All Organocatalysts", with all the summarised papers' catalysts. MHT - good idea.

KAB - Jan22 - (not sure of relevancy) Found "Stereoselectivity of Superacid-Catalyzed Pictet−Spengler Cyclization Reactions." 2003 Ohwada OrgLett (added to DropBox). Proposes dicationic intermediate/transition state(?) mechanism for PS reaction of non-activated aromatics in the presence of catalytic (achiral) acid. MHT - sounds interesting, will check it out.

KAB - Feb11 - Significant discussion of PS mechanism and acid-base effects on non-enzymatic aq solution PS reactions with enzyme cat. reactions, using kinetic isotope effects. RDS appears to be the same for both systems. Discusses pH dependence of enzyme for catalysis but not binding of substrate. Also, proposal of enzyme mechanism with key Glu309, where tryptamine is deprotonated, increasing its nucleophilicity for aldehyde attack. Not sure of how (or if) this is to be spread between mech vs enzyme section?

MAT - Feb11 - KAB, I'm trying to nail down more of the enzymatic "practical uses" in the Enzymatic Catalysis section, but I moved my comment about the OpSTS computation TS to your mechs section. I think, as Mat mentioned, that the catalysis section has to be for actual end-products, so I'll likely write up the NCS generation of benzoisoquinoline nps and O'Connor / Stockigt's work with fluorinated tryptamines for my section.

Also, for anyone who wants to answer, the graphics all have to be open-sourced, right? So I can't clip a xstal structure out of a paper and re-use it here, even if I attribute it to JACS? Please clarify. (KAB reply): are you able to access the PDB, manipulate then export using Jmol? I'm guessing it's enzyme related. (MAT reply): I was going to .pdf snapshot the enzyme overlay from O'Connor JACS 2008 (with the pink and green substrates) to use here, but I likely have to request permission to do so.

Papers that are relevant and need to be included for the first time

These papers are relevant and have not yet been included. They need a summary paragraph and possibly a scheme. Papers that are included need to have their citation data put in the right place in the review, and need to be added to the Mendeley Page. Papers that are not included should be listed in full in the "not-being used" section but do not need to be added to the Mendeley library.

None currently pending

Papers that have not yet been included, but have been referenced by others

These papers need to be checked for relevance. They typically have come from other, relevant papers, but the relevance may not be clear. If they are relevant and need including, move the citation from this section to the "needs to be included" section above. If you wish to then actually include it in the review, write "your initials - doing" next to the paper and start working.

Introduction/Background to the PS Reaction

These general reviews need to be checked, to ensure we have not missed anything, and as inspiration for thoughts on the reaction mechanism.

Current Organic Synthesis 2010 - We have this in Sydney, but access is non-trivial.
Stoeckigt and Waldmann Angew 2011
Pulka, K. Curr. Opin. Drug Discov. Devel. 2010, 13, 669–684 - referenced from Franz 2011 - not easily available (MHT Feb 2) - ignore?

Early examples: probably rac/achiral

Pictet, A.; Spengler, T. Ber. Dtsch. Chem. Ges. 1911, 44, 2030-2036. (DOI: 10.1002/cber.19110440309) Paper
Tatsui, G. J. Pharm. Soc. Jpn. 1928, 48, 92 (may be 453-459).
Cox, E. D.; Cook, J. M. Chem. Rev. 1995, 95, 1797- 1842 (especially their tryptophan ester strategy) (DOI: 10.1021/cr00038a004) Paper
Chrzanowska, M.; Rozwadowska, M. D. Chem. Rev. 2004, 104, 3341-3370. (DOI: 10.1021/cr030692k) Paper
Nature: Naoi, M.; Maruyama, W.; Nagy, G. M. Neurotoxicology 2004, 25, 193- 204 (DOI: 10.1016/S0161-813X(03)00099-8) Paper

Some good medicinal chemistry examples of isatin-derived compounds in Franz 2011 and bencivennia 2011.

Check for the importance of the structural motifs constructed with the reaction:

Brown, R. T. In Indoles; Saxton, J. E., Ed.; Wiley- Interscience: New York, 1983; Part 4 (The Monoterpenoid Indole Alkaloids)
Bentley, K. W. Nat. Prod. Rep. 2004, 21, 395-424 and references therein
W. Jiang, J. Guan, M. J. Macielag, S. Zhang, Y. Qiu, P. Kraft, S. (DOI: 10.1021/jm025545d) Paper

Also possibly: Bhattacharjee, T. M. John, D. Haynes-Johnson, S. Lundeen, Z. Sui, J. Med. Chem. 2005, 48, 2126 – 2133 (DOI: 10.1021/jm0401098) Paper

Specifically with respect to carbolines:

Kawasaki, T.; Higuchi, K. Nat. Prod. Rep. 2005, 22, 761–793 (DOI: 10.1039/B502162F) Paper
Yu, J.; Wang, T.; Liu, X.; Deschamps, J.; Anderson, J. F.; Liao, X.; Cook, J. M. J. Org. Chem. 2003, 68, 7565–7581 (DOI: 10.1021/jo030006h) Paper
Liao, X.; Zhou, H.; Yu, J.; Cook, J. M. J. Org. Chem. 2006, 71, 8884–8890 (DOI: 10.1021/jo061652u) Paper
Ma, J.; Yin, W.; Zhou, H.; Cook, J. M. Org. Lett. 2007, 9, 3491–3494 (DOI: 10.1021/ol071220l) Paper
Herraiz, T. J. Chromatogr. A 2000, 881, 483–499 (DOI: 10.1016/S0021-9673(99)01313-8) Paper
Herraiz, T.; Galisteo, J.; Chamorro, C. J. Agric. Food Chem. 2003, 51, 2168–2173. (DOI: 10.1021/jf0210066) Paper

Diastereoselective examples:

Early diastereoselective, to reference: Ungemach, F.; DiPierro, M.; Weber, R.; Cook, J. M. J. Org. Chem. 1981, 46, 164. (DOI: 10.1021/jo00314a035) Paper

Study to reference: Cox, E. D.; Hamaker, L. K.; Li, J.; Yu, P.; Czerwinski, K. M.; Deng, L.; Bennett, D. W.; Cook, J. M. J. Org. Chem. 1997, 62, 44-61 (DOI: 10.1021/jo951170a) Paper.

To Do:

Czarnocki, Z.; MacLean, D. B.; Szarek, W. A. Can. J. Chem. 1986, 64, 2205-2210. (DOI: 10.1139/v86-363) Paper
Czarnocki, Z.; Suh, D.; MacLean, D. B.; Hultin, P. G.; Szarek, W. A. Can. J. Chem. 1992, 70, 1555-1561. (DOI: 10.1139/v92-191) Paper
Czarnocki, Z.; Mieckzkowsi, J. B.; Kiegiel, J.; Arazn ́y, Z. Tetrahyedron: Asymmetry 1995, 6, 2899-2902. (DOI: 10.1016/0957-4166(95)00380-0) Paper
Tsuji, R.; Nakagawa, M.; Nishida, A. Tetrahedron: Asymmetry 2003, 14, 177- 180. (DOI: 10.1016/S0957-4166(02)00793-0) Paper

Papers relating to indole chemistry in asymmetric catalysis, cited by Bencivennia 2011:

M. Bandini, A. Eicholtzer, Angew. Chem. Int. Ed. 2009, 48, 9608–9644
G. Bartoli, G. Bencivenni, R. Dalpozzo, Chem. Soc. Rev. 2010, 39, 4449 – 4465
T. B. Poulsen, K. A. Jørgensen, Chem. Rev. 2008, 108, 2903 – 2915
E. MarquØs-López, R. P. Herrera, M. Christmann, Nat. Prod. Rep. 2010, 27, 1138 – 1167

Diastereoelective Reactions

Diastereoselective (note: must be catalytic for full inclusion - may be no examples):

Czarnocki, Z.; MacLean, D. B.; Szarek, W. A. Can. J. Chem. 1986, 64, 2205-2210. (DOI: 10.1139/v86-363) Paper
Czarnocki, Z.; Suh, D.; MacLean, D. B.; Hultin, P. G.; Szarek, W. A. Can. J. Chem. 1992, 70, 1555-1561. (DOI: 10.1139/v92-191) Paper
Czarnocki, Z.; Mieckzkowsi, J. B.; Kiegiel, J.; Arazn ́y, Z. Tetrahyedron: Asymmetry 1995, 6, 2899-2902. (DOI: 10.1016/0957-4166(95)00380-0) Paper
Tsuji, R.; Nakagawa, M.; Nishida, A. Tetrahedron: Asymmetry 2003, 14, 177- 180. (DOI: 10.1016/S0957-4166(02)00793-0) Paper

Lewis Acids

Currently have Nakagawa, which is not catalytic. Don't need more examples of reagent-controlled enantioselective PS - only include more Lewis acid examples if very noteworthy or catalytic.

Check:

Hino, T.; Nakagawa, M. Heterocycles 1998, 49, 499-531.
Leighton Angew 2009

Bronsted Acid Section

Akiyama (2004) says these earlier reports "claim" the use of chiral B acids - is that the case, and is the work relevant here?

KAB: Not relevant. Not chiral acid, use of chiral aux. in Diels-Alder. C. Palomo, M. Oiarbide, J. M. Garcia, A. Gonzalez, A. Lecumberri, A. Linden, J. Am. Chem. Soc. 2002, 124, 10288 (DOI: 10.1021/ja025906e) Paper
KAB: relevant. Early use of chiral phosphoric acids (binol and H8-binol) in enantioselective Morita-Baylis-Hillman reaction. N. T. McDougal, S. E. Schaus, J. Am. Chem. Soc. 2003, 125, 12094 (DOI: 10.1021/ja037705w) Paper MHT - that sounds very relevant - a year before Akiyama/Terada. Needs to be properly included? KAB Jan23 - Probably. It's a bit different to the rest. Acids were catalytic, but also required a "nucleophilic promotor." Not sure what that is, but it was present in less than stoich amounts as well.
KAB: not quite relevant. Uses H-bond activation via chiral TADDOL, in highly enantioselective Hetero-Diels-Alder. Y. Huang, A. K. Unni, A. N. Thadani, V. H. Rawal, Nature 2003, 424, 146. MHT - sure, but why is this paper in Nature? What is it showing that is so important, and does this need to be mentioned in the mech section?

Akiyama (2004) also mentions these "metal salt" versions:

J. Inanaga, Y. Sugimoto, T. Hanamoto, New J. Chem. 1995, 19, 707
H. Furuno, T. Hanamoto, Y. Sugimoto, J. Inanaga, Org. Lett. 2000, 2, 49 (DOI: 10.1021/ol991189q) Paper

Previous Bronsted acid example from Terada

Huang, Y.; Unni, A. K.; Thadani, A. N.; Rawal, V. H. Nature 2003, 424, 146.
McDougal, N. T.; Schaus, S. E. J. Am. Chem. Soc. 2003,125, 12094.

Example of chiral charged Brønsted acid catalyst:

Nugent, B. M.; Yoder, R. A.; Johnston, J. N. J. Am. Chem. Soc. 2004,126, 3418.

Jacobsen Strecker and Mannich history, from Terada

Sigman, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 4901.
Vachal, P.; Jacobsen, E. N. Org. Lett. 2000, 2, 867.
Sigman, M. S.; Vachal, P.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2000, 39, 1279.
Su, J. T.; Vachal, P.; Jacobsen, E. N. AdV. Synth. Catal. 2001, 343, 197.
Vachal, P.; Jacobsen, E. N. J. Am. Chem. Soc. 2002, 124, 10013.
Wenzel, A. G.; Lalonde, M. P.; Jacobsen, E. N. Synlett 2003, 1919.
Wenzel, A. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2002, 124, 12964.

Organocatalysis Section

Check for relevancy:

Metal-free organocatalysis through explicit hydrogen bonding interactions, Schreiner, P. R. Chem. Soc. ReV. 2003, 32, 289. (DOI:10.1039/b107298) - KAB: Not B Acids. On Thio-Urea.
(Thio)urea organocatalysis—What can be learnt from anion recognition?, Z. Zhang, P. Schreiner, Chem. Soc. Rev. 2009, 38, 1187 – 1198 (DOI: 10.1039/B801793J) Paper - KAB: Not on B acids. Thio-urea stuff.

Not looked at to see which section these go in:

Asymmetric Bronsted Acid Catalyzed Nucleophilic Addition to in situ Generated Chiral N-Acyliminium Ions, Rueping, M.; Nachtsheim, B. J. Synlett 2010, 1, 119. (DOI: 10.1055/s-0029-1218539) - KAB: Probably needs to go in the B acid section.
Peterson, E. A.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2009, 48, 6328.
Raheem, I. T.; Thiara, P. S.; Jacobsen, E. N. Org. Lett. 2008, 10, 1577
Sun, F.-L.; Zheng, X.-J.; Gu, Q.; He, Q.-L.; You, S.-L. Eur. J. Org. Chem. 2010, 47

Mechanism section

Some possibly relevant papers arising from Dixon 2010, on chiral counterion-induced enantioselective N-acyliminium ion reactions:

Li, G.; Kaplan, M. J.; Wojtas, L.; Antilla, J. C. Org. Lett. 2010, 12, 1960.
Terada, M.; Machioka, K.; Sorimachi, K. Angew. Chem., Int. Ed. 2009, 48, 2553.
Rueping, M.; Lin, M.-Y. Chem.sEur. J. 2010, 16, 4169.

Some papers on dual catalysis referenced by Franz 2011:

Yamamoto, H.; Futatsugi, K. Angew. Chem., Int. Ed. 2005, 44, 1924–1942
Lv, J.; Li, X.; Zhong, L.; Luo, S.; Cheng, J.-P. Org. Lett. 2010, 12, 1096–1099
Rueping, M.; Koenigs, R. M.; Atodiresei, I. Chem. Eur. J. 2010, 16, 9350–9365.

Other Relevant Systems not yet applied to the PS

Check these papers for possible suitability for the PS, and check that they have not been so-used. The aim is to say in the review which catalysts show promise but are unexplored.

Strong Bronsted acids not yet applied to PS:

Chiral N-triflyl phosphoramide Yamamoto 2006

Check:

C. H. Cheon, H. Yamamoto, J. Am. Chem. Soc. 2008, 130, 9246–9247 (DOI: 10.1021/ja8041542) Paper
C. H. Cheon, H. Yamamoto, Org. Lett. 2010, 12, 2476–2479 (DOI: 10.1021/ol100233t) Paper
M. Rueping, W. Ieawsuwan, A. P. Antonchick, B. J. Nacht- sheim, Angew. Chem. Int. Ed. 2007, 46, 2097–2100 (DOI: 10.1002/anie.200604809) Paper
P. Jiao, D. Nakashima, H. Yamamoto, Angew. Chem. Int. Ed. 2008, 47, 2411–2413 (DOI: 10.1002/anie.200705314) Paper
H. Xu, S. J. Zuend, M. G. Woll, Y. Tao, E. N. Jacobsen, Science 2010, 327, 986–990 (mixture).
M. Treskow, J. Neudörfl, R. Giernoth, Eur. J. Org. Chem. 2009, 3693–3697.
P. García-García, F. Lay, P. García-García, C. Rabalakos, B. List, Angew. Chem. Int. Ed. 2009, 48, 4363–4366.

TADDOL ligands:

Akiyama 2005
(TADDOL activator) Rawal 2003

Enzymatic examples: (Working on, MAT)

Norcoclaurine synthase Tanner 2007
Strictosidine Synthase Stoeckigt 2008
Deacetylipecoside Synthase - need ref if this is a relevant enzyme

Papers that may use the cat, asymm PS in syntheses, to be checked

MAT - Jan 30 - Per Sanjay's request, a Reaxys search for "asymmetric Pictet-Spengler" returns 110 hits, and "catalytic asymmetric Pictet-Spengler" returns only 9. In the former, several recent syntheses we haven't yet addressed (saframycin, alstoscholarine, polyneuridine) may need to be checked to see if they incorporate catalytic methodology to set stereochem (currently looking through syntheses - MAT Feb 11)

Simple items to do

MHT - Jan21 - Need people to go through all the references on this page and insert a DOI link for ease of access.

Quality Control

All papers included in the main text of the review will have been summarised by one person. The summary (text and scheme) need to be checked by at least one other person - that means going back to the primary literature source. This section contains a list of who has done what.

Arrange list in approximate order of appearance in review.

Nakagawa 1998 (10.1021/jo980810h) - written by MNR, not yet checked.
Akiyama (10.1002/anie.200353240) - written by MHT, not yet checked.
Terada (10.1021/ja0491533) - written by MHT, not yet checked.
List 2006 (10.1021/ja057444l) - written by MHT, not yet checked.
Hiemstra 2007 (10.1002/anie.200701808) - written by KAB, checked by MNR & MHT.
Hiemstra 2008 (10.1021/jo8010478) - written by KAB, checked by MNR & MHT.
Hiemstra 2009 (10.1021/ol900888e) - written by MHT, not yet checked.
Hiemstra 2011 (10.1021/jo201657n) - written by MHT, not yet checked.
Dixon 2009 (10.1021/ja9024885) - written by MHT, not yet checked.
Dixon 2010 (10.1021/ol101651t) - written by KAB, checked and rewritten by MHT - needs further check.
Franz 2011 (10.1016/j.tetlet.2011.08.071) - written by MNR, significantly re-worked by MHT - needs further check.
Jacobsen 2004 - written by MNR, checked and rewritten by MAT - needs recheck.
Jacobsen 2007 - written by MNR, not yet checked.
Jacobsen 2007 review - written by MNR, not yet checked.
Jacobsen 2008 - written by MNR, not yet checked.
Jacobsen 2009 - written by MNR, not yet checked.
Jacobsen 2011 - written by MNR, not yet checked.

Resolved

KAB - Jan21 - The scheme for 2009 Hiemstra with the H8-BINOL phosphoric acid in the box, doesn't have the H8-BINOL phosphoric acid in the box. Still has the BINOL. (KAB: fixed in the chemdraw file and re-uploaded the png, but it is yet show the change in the review.) - KAB, done.

1. KAB attempt to understand 2000 Koomen OrgLett The figure for Table 1 gives diasteromeric ratios. Where are the diastereomers? I only the possibility for enantiomers in the product. Where's the other stereogenic centre? They also mentioned "hydrolysis of the starting material" numerous times. I'm assuming they mean hydrolysis of the N-S bond (there doesn't seem any other reasonable place for hydrolysis of the SM to occur), but I just wanted to check. This comment resolved since this paper no longer included in the review.

MHT - Jan 22 - Reworked Dixon 2010 into one scheme. KAB please check and comment. KAB: Neater. Is the formation of the enamide intermediates reversible? I was under the impression the first condensation was irreversible. So forego the "best" result, in terms of ee and yield and instead incorporate the mech into the scheme? MHT: I doubt enamide formation is reversible (in its entirety) but it's a toluene reflux, so might be worth erring on the side of caution. And yes - I have foregone the "best" result here so we can combine mechanism and reaction outcome in one. Typical yield/ee mentioned in text.

MHT - Jan21 - Do we have a significant section on enzyme examples, or do we refer to the 2011 Waldmann review, which appears to cover this well? I would favour a brief description, with the value being clues we learn about the mechanism of catalysis, and whether we can apply those lessons to small molecule catalysis. Resolved because enzyme section now included, with emphasis on preparative utility and, in a separate section, an emphasis on what we learn about the mechanisms of the enzyme-catalyzed reactions.

MAT - Jan 29 - Can someone tell me how to be added to the review DropBox? I have the program installed, but I can't seem to access the folder. (Mendeley works just fine, btw) Resolved - Murray has added Mike to the shared "Pictet-Spengler Review" folder

SB - Feb 06 - In the review Leighton Angew 2009 the chiral chlorosilanes are used in quatitative ratio and not in catalytic amount.

MAT - Feb 11 - Natural product synthesis - hongconin and thysanone use Oxa-Pictet-Spengler, non-catalytic. Do not include.

MAT - Feb11 - Can someone grab the Nature 2010, p.461 O'Connor paper and place it in Dropbox? It's crucial for the enzyme section (no easy access to Nature here!) KAB Added to dropbox

KAB - Jan22 - Need to annotate Dixon 2010 Cyclisation Cascade with keq's and kminor and kmajor - but MHT has altered this scheme, and I don't think the k's add anything.

Talk:Todd:Catalytic, Asymmetric Pictet-Spengler Reaction

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