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. We are currently (Jan21) working on a Dropbox solution to share papers and file between authors - to be resolved.

General Comments, either on science or the review more broadly

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 - 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.

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.

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.

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.

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

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

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.

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.
• Czarnocki, Z.; Suh, D.; MacLean, D. B.; Hultin, P. G.; Szarek, W. A. Can. J. Chem. 1992, 70, 1555-1561.
• Czarnocki, Z.; Mieckzkowsi, J. B.; Kiegiel, J.; Arazn ́y, Z. Tetrahyedron: Asymmetry 1995, 6, 2899-2902.
• Tsuji, R.; Nakagawa, M.; Nishida, A. Tetrahedron: Asymmetry 2003, 14, 177- 180.

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
• 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
• 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.

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

Previous Bronsted acid example from Terada

• Schreiner, P. R. Chem. Soc. ReV. 2003, 32, 289.
• 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.

See also:

• Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003, 125, 12672.
• Okino, T.; Nakamura, S.; Furukawa, T.; Takemoto,Y. Org. Lett. 2004, 6, 625.

Copper complex example from Terada:

• Marigo, M.; Kjærsgaard, A.; Juhl, K.; Gathergood, N.; Jørgensen, K. A. Chem.- Eur. J. 2003, 9, 2359.

The strengths of these chiral phosphoric acids is governed by:

• Akiyama Chem Rev 2007
• Terada ChemComm 2008

Reviews to check through for comments on mechanism of reactions and possible applications of Bronsted acids that have not yet been applied to the PS.

• S.J. Connon, Angew. Chem. Int. Ed. 2006, 45, 3909–3912
• T. Akiyama, J. Itoh, K. Fuchibe, Adv. Synth. Catal. 2006, 348, 999 – 1010
• M. S. Taylor, E. N. Jacobsen, Angew. Chem. Int. Ed. 2006, 45, 1520–1543
• Connon, S. J. Org. Biomol. Chem. 2007, 5, 3407–3417
• Terada Synthesis 2010, 1929-1982
• List, Top. Curr. Chem. 2010, 291, 395-456
• Rueping Angewandte 2011, 50, 6706-6720

Organocatalysis Section

None pending

Mechanism section

None pending

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
  
• C. H. Cheon, H. Yamamoto, Org. Lett. 2010, 12, 2476–2479
  
• M. Rueping, W. Ieawsuwan, A. P. Antonchick, B. J. Nacht- sheim, Angew. Chem. Int. Ed. 2007, 46, 2097–2100
  
• P. Jiao, D. Nakashima, H. Yamamoto, Angew. Chem. Int. Ed. 2008, 47, 2411–2413.
  
• 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:

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

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.
  
• KAB - Jan22 - Need to annotate Dixon 2010 Cyclisation Cascade with keq's and kminor and kmajor.

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, not yet checked.
  
• Franz 2011 (10.1016/j.tetlet.2011.08.071) - written by MNR, not yet checked.
  
• Jacobsen 2004 - written by MNR, not yet checked.
  
• 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. --