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DOI: 10.1055/s-0031-1290107
The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis
Publication History
Publication Date:
09 December 2011 (online)

Abstract
The Hajos-Parrish-Eder-Sauer-Wiechert reaction can be considered as the origin of asymmetric organocatalysis, giving rise to the Wieland-Miescher ketone 1 (WMK), a versatile building block. Although 40 years have passed since its discovery, a highly enantioselective and scalable synthesis of the WMK has remained elusive. This account details a solution to that problem that came about in the development of methodology towards C-8a WMK analogues as part of the total synthesis of complex diterpene natural products. The work has been placed in the context of the historical background and reactivity of this important building block, highlighting the challenges faced by organocatalysis in large-scale reactions.
1 Introduction
2 The Wieland-Miescher Ketone
2.1 The Hajos-Parrish-Eder-Sauer-Wiechert Reaction: A Historical Perspective
2.2 Practicalities of the Wieland-Miescher Ketone Synthesis Using Proline
2.3 Alternative Catalysts for the Synthesis of the Wieland-Miescher Ketone
3 Background to Developing a New Wieland-Miescher Ketone Synthesis
4 Optimization of Method and Conditions
5 Key Reactions of the Wieland-Miescher Ketone
5.1 Reduction, Oxidation, Protection, and Non-C-C-Bond-Forming Reactions
5.2 C-C-Bond-Forming Reactions
5.3 Ring-Expansion and -Contraction Reactions
6 Conclusions and Future Considerations
Key words
Wieland-Miescher ketone - enantioselective direct aldol reaction - asymmetric organocatalysis - total synthesis - natural products
- 1
List B.Lerner RA.Barbas CF. J. Am. Chem. Soc. 2000, 122: 2395Reference Ris Wihthout Link - 2
Ahrendt KA.Borths CJ.MacMillan DWC. J. Am. Chem. Soc. 2000, 122: 4243Reference Ris Wihthout Link - 3
Bertelsen S.Jørgensen KA. Chem. Soc. Rev. 2009, 38: 2178Reference Ris Wihthout Link - 4a
Hajos ZG, andParrish DR. inventors; DE 2102623.Reference Ris Wihthout Link - 4b
Eder U,Sauer GR, andWiechert R. inventors; DE 2014757.Reference Ris Wihthout Link - 4c
Eder U.Sauer GR.Wiechert R. Angew. Chem., Int. Ed. Engl. 1971, 10: 496 ; Angew. Chem. 1971, 83, 492Reference Ris Wihthout Link - 4d
Hajos ZG.Parrish DR. J. Org. Chem. 1974, 39: 1615Reference Ris Wihthout Link - 5
MacMillan DWC. Nature 2008, 455: 304Reference Ris Wihthout Link - 6
Barbas CF. Angew. Chem. Int. Ed. 2008, 47: 42Reference Ris Wihthout Link - 7a
Corey EJ.Ohno M.Vatakencherry PA.Mitra RB. J. Am. Chem. Soc. 1961, 83: 1251Reference Ris Wihthout Link - 7b
Corey EJ.Ohno M.Mitra RB.Vatakencherry PA. J. Am. Chem. Soc. 1964, 86: 478Reference Ris Wihthout Link - 7c
Piers E.Britton RW.De Waal W. J. Chem. Soc. D 1969, 1069Reference Ris Wihthout Link - 7d
Piers E.De Waal W.Britton RW. J. Am. Chem. Soc. 1971, 93: 5113Reference Ris Wihthout Link - 7e
Heathcock CH.DelMar EG.Graham SL. J. Am. Chem. Soc. 1982, 104: 1907Reference Ris Wihthout Link - 7f
Smith AB.Mewshaw R. J. Org. Chem. 1984, 49: 3685Reference Ris Wihthout Link - 7g
Shishido K.Tokunaga Y.Omachi N.Hiroya K.Fukumoto K.Kametani T.
J. Chem. Soc., Chem. Commun. 1989, 1093Reference Ris Wihthout Link - 7h
Smith AB.Sunazuka T.Leenay TL.Kingery-Wood J. J. Am. Chem. Soc. 1990, 112: 8197Reference Ris Wihthout Link - 7i
Smith AB.Kingery-Wood J.Leenay TL.Nolen EG.Sunazuka T. J. Am. Chem. Soc. 1992, 114: 1438Reference Ris Wihthout Link - 7j
Grieco PA.Collins JL.Moher ED.Fleck TJ.Gross RS. J. Am. Chem. Soc. 1993, 115: 6078Reference Ris Wihthout Link - 7k
Paquette LA.Wang T.Philippo CMG.Wang S. J. Am. Chem. Soc. 1994, 116: 3367Reference Ris Wihthout Link - 7l
Ziegler FE.Wallace OB. J. Org. Chem. 1995, 60: 3626Reference Ris Wihthout Link - 7m
Dzierba CD.Zandi KS.Möllers T.Shea KJ. J. Am. Chem. Soc. 1996, 118: 4711Reference Ris Wihthout Link - 7n
Danishefsky SJ.Masters JJ.Young WB.Link JT.Snyder LB.Magee TV.Jung DK.Isaacs RCA.Bornmann WG.Alaimo CA.Coburn CA.Di Grandi MJ. J. Am. Chem. Soc. 1996, 118: 2843Reference Ris Wihthout Link - 7o
Stork G.West F.Lee HY.Isaacs RCA.Manabe S. J. Am. Chem. Soc. 1996, 118: 10660Reference Ris Wihthout Link - 7p
An J.Wiemer DF. J. Org. Chem. 1996, 61: 8775Reference Ris Wihthout Link - 7q
Paquette LA.Backhaus D.Braun R.Underiner TL.Fuchs K. J. Am. Chem. Soc. 1997, 119: 9662Reference Ris Wihthout Link - 7r
Harada N.Sugioka T.Ando Y.Uda H.Kuriki T. J. Am. Chem. Soc. 1988, 110: 8483Reference Ris Wihthout Link - 7s
Kurosu M.Marcin LR.Grinsteiner TJ.Kishi Y. J. Am. Chem. Soc. 1998, 120: 6627Reference Ris Wihthout Link - 7t
Karimi S.Tavares P. J. Nat. Prod. 2003, 66: 520Reference Ris Wihthout Link - 7u
Kende AS.Deng W.Zhong M.Guo X. Org. Lett. 2003, 5: 1785Reference Ris Wihthout Link - 7v
Deng W.Zhong M.Guo X.Kende AS. J. Org. Chem. 2003, 68: 7422Reference Ris Wihthout Link - 7w
Smith AB.Kanoh N.Ishiyama H.Minakawa N.Rainier JD.Hartz RA.Cho YS.Cui H.Moser WH. J. Am. Chem. Soc. 2003, 125: 8228Reference Ris Wihthout Link - 7x
Waters SP.Tian Y.Li Y.Danishefsky SJ. J. Am. Chem. Soc. 2005, 127: 13514Reference Ris Wihthout Link - 7y
Díaz S.González A.Bradshaw B.Cuesta J.Bonjoch J. J. Org. Chem. 2005, 70: 3749Reference Ris Wihthout Link - 7z
Peng X.Wong HNC. Chem. Asian J. 2006, 1: 111Reference Ris Wihthout Link - (aa)
Ferraz HMC.Souza AJC.Tenius BSM.Bianco GG. Tetrahedron 2006, 62: 9232Reference Ris Wihthout Link - (ab)
Chanu A.Safir I.Basak R.Chiaroni A.Arseniyadis S. Org. Lett. 2007, 9: 1351Reference Ris Wihthout Link - (ac)
Hanessian S.Boyer N.Reddy GJ.Deschênes-Simard B. Org. Lett. 2009, 11: 4640Reference Ris Wihthout Link - (ad)
Carneiro VMT.Ferraz HMC.Vieira TO.Ishikawa EE.Silva LF. J. Org. Chem. 2010, 75: 2877Reference Ris Wihthout Link - For other syntheses of natural products from the Wieland-Miescher ketone not depicted in Figure 1, see:
- 8a bulnesene:
Heathcock CH.Ratcliffe R. J. Am. Chem. Soc. 1971, 93: 1746Reference Ris Wihthout Link - 8b longifolene:
McMurry JE.Isser SJ. J. Am. Chem. Soc. 1972, 94: 7132Reference Ris Wihthout Link - 8c muzigadial:
Bosch MP.Camps F.Coll J.Guerrero A.Tatsuoka T.Meinwald J. J. Org. Chem. 1986, 51: 773Reference Ris Wihthout Link - 8d paspaline:
Mewshaw RE.Taylor MD.Smith AB. J. Org. Chem. 1989, 54: 3449Reference Ris Wihthout Link - 8e phytocassane D:
Yajima A.Mori K. Eur. J. Org. Chem. 2000, 4079Reference Ris Wihthout Link - 8f longifolene:
Karimi S.Tavares P. J. Nat. Prod. 2003, 66: 520Reference Ris Wihthout Link - 8g 21-isopentenylpaxilline:
Smith AB.Cui H. Org. Lett. 2003, 5: 587Reference Ris Wihthout Link - 8h nodulisporic acid F:
Smith AB.Davulcu AH.Kürti L. Org. Lett. 2006, 8: 1665Reference Ris Wihthout Link - 8i integric acid:
Waalboer DCJ.van Kalkeren HA.Schaapman MC.van Delft FL.Rutjes FPJT. J. Org. Chem. 2009, 74: 8878Reference Ris Wihthout Link - 8j carainterol A:
Ma K.Zhang C.Liu M.Chu Y.Zhou L.Hu C.Ye D. Tetrahedron Lett. 2010, 51: 1870Reference Ris Wihthout Link - 9 For a detailed overview see:
Mukherjee S.Yang JW.Hoffmann S.List B. Chem. Rev. 2007, 107: 5471Reference Ris Wihthout Link - 10
Wieland P.Miescher K. Helv. Chim. Acta 1950, 33: 2215Reference Ris Wihthout Link - For other racemic approaches to the Wieland-Miescher ketone see
- 11a
Wendler NL.Slates HL.Tishler M.
J. Am. Chem. Soc. 1951, 73: 3816Reference Ris Wihthout Link - 11b
Sondheimer F.Elad D. J. Am. Chem. Soc. 1957, 79: 5542Reference Ris Wihthout Link - 11c
Swaminathan S.Newman MS. Tetrahedron 1958, 2: 88Reference Ris Wihthout Link - 11d
Newman MS.Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039Reference Ris Wihthout Link - 11e
Newman MS.Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039Reference Ris Wihthout Link - 11f
Mekler AB.Ramachandran S.Swaminathan S.Newman MS. Org. Synth. Coll. Vol. V John Wiley & Sons; London: 1973. p.743 ; Org. Synth. 1961, 41, 56Reference Ris Wihthout Link - 11g
Sondheimer F.Elad D.
J. Am. Chem. Soc. 1957, 79: 5542Reference Ris Wihthout Link - 12a
Bahmanyar S.Houk KN. J. Am. Chem. Soc. 2001, 123: 11273Reference Ris Wihthout Link - 12b
Bahmanyar S.Houk KN.Martin HJ.List B. J. Am. Chem. Soc. 2003, 125: 2475Reference Ris Wihthout Link - 13a
Stork G.Brizzolara A.Landesman H.Szmuszkovicz J.Terrell R. J. Am. Chem. Soc. 1963, 85: 207Reference Ris Wihthout Link - 13b
Stork G.Saccomano NA. Tetrahedron Lett. 1987, 28: 2087Reference Ris Wihthout Link - 13c
The Chemistry
of Enamines
Rappoport Z. Wiley; New York: 1994.Reference Ris Wihthout Link - 14
Machajewski TD.Wong C.-H. Angew. Chem. Int. Ed. 2000, 39: 1352Reference Ris Wihthout Link - 15
Jung ME. Tetrahedron 1976, 32: 3Reference Ris Wihthout Link - 16
List B.Hoang L.Martin HJ. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 5839Reference Ris Wihthout Link - 17a
Puchot C.Samuel O.Dunach E.Zhao S.Agami C.Kagan HB. J. Am. Chem. Soc. 1986, 108: 2353Reference Ris Wihthout Link - 17b
Agami C.Meynier F.Puchot C.Guilhem J.Pascard C. Tetrahedron 1984, 40: 1031Reference Ris Wihthout Link - 18
Hoang L.Bahmanyar S.Houk KN.List B. J. Am. Chem. Soc. 2003, 125: 16Reference Ris Wihthout Link - 19
Rajagopal D.Moni MS.Subramanian S.Swaminathan S. Tetrahedron: Asymmetry 1999, 10: 1631Reference Ris Wihthout Link - 20a
Bui T.Barbas CF. Tetrahedron Lett. 2000, 41: 6951Reference Ris Wihthout Link - For a modified approach using MeCN as the solvent see:
- 20b
Lazarski KE.Rich AA.Mascarenhas CM.
J. Chem. Educ. 2008, 85: 1531Reference Ris Wihthout Link - 21
Gutzwiller J.Buchschacher P.Fürst A. Synthesis 1977, 167Reference Ris Wihthout Link - 22
Buchschacher P.Fürst A. Org. Synth. 1985, 63: 3743Reference Ris Wihthout Link - 23
Harada N.Sugioka T.Uda H.Kuriki T. Synthesis 1990, 53Reference Ris Wihthout Link - 24
Tietze LF.Utecht J. Synthesis 1993, 957Reference Ris Wihthout Link - 25a
Hioki H.Hashimoto T.Kodama M. Tetrahedron: Asymmetry 2000, 11: 829Reference Ris Wihthout Link - 25b
Fuhshuku K.Funa N.Akeboshi T.Ohta H.Hosomi H.Ohba S.Sugai T.
J. Org. Chem. 2000, 65: 129Reference Ris Wihthout Link - 25c
Fuhshuku K.Tomita M.Sugai T. Adv. Synth. Catal. 2003, 345: 766Reference Ris Wihthout Link - 26
Kasai Y.Shimanuki K.Kuwahara S.Watanabe M.Harada N. Chirality 2006, 18: 177Reference Ris Wihthout Link - 27
Zhong G.Hoffmann T.Lerner RA.Danishefsky S.Barbas CF. J. Am. Chem. Soc. 1997, 119: 8131Reference Ris Wihthout Link - 28a
Davies SG.Sheppard RL.Smith AD.Thomson JE. Chem. Commun. 2005, 3802Reference Ris Wihthout Link - 28b
Davies SG.Russell AJ.Sheppard RL.Smith AD.Thomson JE. Org. Biomol. Chem. 2007, 5: 3190Reference Ris Wihthout Link - 29
Lacoste E.Vaique E.Berlande M.Pianet I.Vincent J.Landais Y. Eur. J. Org. Chem. 2007, 167Reference Ris Wihthout Link - 30a
Akahane Y.Inage N.Nagamine T.Inomata K.Endo Y. Heterocycles 2007, 74: 637Reference Ris Wihthout Link - 30b
Note catalyst 11 was first introduced by Barbas in a one-pot version where it was observed that without the presence of acid no dehydration took place, see ref. 20.
Reference Ris Wihthout Link - 31a
Kanger T.Kriis K.Laars M.Kailas T.Müürisepp A.Pehk T.Lopp M. J. Org. Chem. 2007, 72: 5168Reference Ris Wihthout Link - 31b
Laars M.Kriis K.Kailas T.Müürisepp A.Pehk T.Kanger T.Lopp M. Tetrahedron: Asymmetry 2008, 19: 641Reference Ris Wihthout Link - 32
D’Elia V.Zwicknagl H.Reiser O. J. Org. Chem. 2008, 73: 3262Reference Ris Wihthout Link - 33
Guillena G.Nájera C.Viózquez SF. Synlett 2008, 3031Reference Ris Wihthout Link - 34
Almaºi D.Alonso DA.Nájera C. Adv. Synth. Catal. 2008, 350: 2467Reference Ris Wihthout Link - 36
Zhang X.Wang M.Tu Y.Fan C.Jiang Y.Zhang S.Zhang F. Synlett 2008, 2831Reference Ris Wihthout Link - 37
Fuentes de Arriba L.Simón L.Raposo C.Alcázar V.Morán JR. Tetrahedron 2009, 65: 4841Reference Ris Wihthout Link - 39a
Akahane Y.Inomata K.Endo Y. Heterocycles 2009, 77: 1065Reference Ris Wihthout Link - 39b
Akahane Y.Inomata K.Endo Y. Heterocycles 2011, 82: 1727Reference Ris Wihthout Link - 40
Fuentes de Arriba L.Seisdedos DG.Simón L.Alcázar V.Raposo C.Morán JR. J. Org. Chem. 2010, 75: 8303Reference Ris Wihthout Link - 41
Díaz S.Cuesta J.González A.Bonjoch J. J. Org. Chem. 2003, 68: 7400Reference Ris Wihthout Link - 42
Gloer JB.Rinderknecht BL.Wicklow DT.Dowd PF. J. Org. Chem. 1989, 54: 2530Reference Ris Wihthout Link - 43
TePaske MR.Gloer JB.Wicklow DT.Dowd PF. J. Org. Chem. 1989, 54: 4743Reference Ris Wihthout Link - 44
Gloer JB.TePaske MR.Sima JS.Wicklow DT.Dowd PF. J. Org. Chem. 1988, 53: 5457Reference Ris Wihthout Link - 45
Staub GM.Gloer JB.Wicklow DT.Dowd PF.
J. Am. Chem. Soc. 1992, 114: 1015Reference Ris Wihthout Link - 46 For an approach to aflavinine 24 see:
Danishefsky S.Chackalamannil S.Harrison P.Silvestri M.Cole P.
J. Am. Chem. Soc. 1985, 107: 2474Reference Ris Wihthout Link - 47a
Liu Y.McWhorter WW.Hadden CE. Org. Lett. 2003, 5: 333Reference Ris Wihthout Link - 47b
Ho GA.Nouri DH.Tantillo DJ. Tetrahedron Lett. 2009, 50: 1578Reference Ris Wihthout Link - 47c
Marcos IS.Moro RF.Costales I.Escola MA.Basabe P.Díez D.Urones JG. Tetrahedron 2009, 65: 10235Reference Ris Wihthout Link - 48a
Crow WD. Aust. J. Chem. 1962, 15: 159Reference Ris Wihthout Link - 48b
Fridrichsons J.Mathieson AMcL. Tetrahedron Lett. 1960, 1: 18Reference Ris Wihthout Link - 48c
Fridrichsons J.Mathieson AMcL. Acta Crystallogr. 1963, 16: 206Reference Ris Wihthout Link - 49
Iwagawa T.Kaneko M.Okamura H.Nakatani M.van Soest RWM. J. Nat. Prod. 1998, 61: 1310Reference Ris Wihthout Link - 50
Johnson TA.Amagata T.Sashidhara KV.Oliver AG.Tenney K.Matainaho T.Ang KK.McKerrow JH.Crews P. Org. Lett. 2009, 11: 1975Reference Ris Wihthout Link - 51
Díaz S.González A.Bradshaw B.Cuesta J.Bonjoch J. J. Org. Chem. 2005, 70: 3749Reference Ris Wihthout Link - 52 For other examples of the difficulty
of 1,4 addition to the WMK 1 see:
Streuff J. Chem.-Eur. J. 2011, 17: 5507Reference Ris Wihthout Link - 53
Lipshutz BH.Ellsworth EL. J. Am. Chem. Soc. 1990, 112: 7440Reference Ris Wihthout Link - 54a
Kwiatkowski S.Syed A.Brock CP.Watt DS. Synthesis 1989, 818Reference Ris Wihthout Link - 54b
Hanselmann R.Benn M. Synth. Commun. 1996, 26: 945Reference Ris Wihthout Link - For an alternative synthesis of the allyl WMK analogue see:
- 54c
Hiroya K.Takahashi T.Shimomae K.Sakamoto T. Chem. Pharm. Bull. 2005, 53: 207Reference Ris Wihthout Link - 54d
Inomata K.Barragué M.Paquette LA. J. Org. Chem. 2005, 70: 533Reference Ris Wihthout Link - 54e
Ramachary DB.Kishor M.
J. Org. Chem. 2007, 72: 5056Reference Ris Wihthout Link - For examples of WMK analogues in total synthesis see:
- 55a
ref. 7l.
Reference Ris Wihthout Link - 55b
Hamilton RJ.Mander LN.Sethi SP. Tetrahedron 1986, 42: 2881Reference Ris Wihthout Link - 55c
Nicolaou KC.Roecker AJ.Monenschein H.Guntupalli P.Follmann M. Angew. Chem. Int. Ed. 2003, 42: 3637Reference Ris Wihthout Link - 56
Prakash C.Mohanakrishnan AK. Eur. J. Org. Chem. 2008, 1535Reference Ris Wihthout Link - 57
Rajamannar T.Palani N.Balasubramanian K. Synth. Commun. 1993, 23: 3095Reference Ris Wihthout Link - 58
Inomata K.Barragué M.Paquette LA. J. Org. Chem. 2005, 70: 533Reference Ris Wihthout Link - 59
Kennedy JWJ.Vietrich S.Weinmann H.Brittain DEA. J. Org. Chem. 2008, 73: 5151Reference Ris Wihthout Link - 60
Piers E.Grierson JR. J. Org. Chem. 1977, 42: 3755Reference Ris Wihthout Link - 62
Birch AJ. J. Chem. Soc. 1947, 102Reference Ris Wihthout Link - 63
Vidari G.Lanfranchi G.Masciaga F.Moriggi J. Tetrahedron: Asymmetry 1996, 7: 3009Reference Ris Wihthout Link - 64
Bradshaw B.Etxebarría-Jardi G.Bonjoch J.Viózquez S.Guillena G.Nájera C. Adv. Synth. Catal. 2009, 351: 2482Reference Ris Wihthout Link - 66 The use of solvents resulted in
very poor reactivity and significantly reduced enantioselectivity.
For an early solvent free organocatalytic reaction using proline
see:
Rajagopal D.Rajagopalan K.Swaminathan S. Tetrahedron: Asymmetry 1996, 7: 2189Reference Ris Wihthout Link - 67
Viózquez S.Guillena G.Nájera C.Bradshaw B.Etxebarría-Jardi G.Bonjoch J. Org. Synth. 2011, 88: 317Reference Ris Wihthout Link - 68
Etxebarria-Jardí G. Ph.D Thesis University of Barcelona; Spain: 2010.Reference Ris Wihthout Link - 69
Bradshaw B.Etxebarria-Jardí G.Bonjoch J. J. Am. Chem. Soc. 2010, 132: 5966Reference Ris Wihthout Link - 70
Bradshaw B.Etxebarría-Jardi G.Bonjoch J.Viózquez S.Guillena G.Nájera C. Org. Synth. 2011, 88: 330Reference Ris Wihthout Link - 71
Walji AM.MacMillan DWC. Synlett 2007, 1477Reference Ris Wihthout Link - 72
Ward DE.Rhee CK.Zoghaib WM. Tetrahedron Lett. 1988, 29: 517Reference Ris Wihthout Link - 73
Sarkar DC.Das AR.Ranu BC. J. Org. Chem. 1990, 55: 5799Reference Ris Wihthout Link - 74
Midland MM.McLoughlin JI.Gabriel J. J. Org. Chem. 1989, 54: 159Reference Ris Wihthout Link - 75
Andrews GC.Crawford TC. Tetrahedron Lett. 1980, 21: 693Reference Ris Wihthout Link - 76
Ley SV.Antonello A.Balskus EP.Booth DT.Christensen SB.Cleator E.Gold H.Högenauer K.Hünger U.Myers RM.Oliver SF.Simic O.Smith MD.Søhoel H.Woolford AJA. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 12073Reference Ris Wihthout Link - 77
Van Gool M.Vandewalle M. Eur. J. Org. Chem. 2000, 3427Reference Ris Wihthout Link - 78
Banerjee A.Poon PS.Laya M. Synth. Commun. 2003, 33: 1929Reference Ris Wihthout Link - 79
Ramachary DB.Sakthidevi R. Org. Biomol. Chem. 2008, 6: 2488Reference Ris Wihthout Link - 80
Ito H.Ishizuka T.Arimoto K.Miura K.Hosomi A. Tetrahedron Lett. 1997, 38: 8887Reference Ris Wihthout Link - 81
von Holleben MLA.Zucolotto M.Zini CA.Oliveira ER. Tetrahedron 1994, 50: 973Reference Ris Wihthout Link - 82
Park K.Scott WJ.Wiemer DF. J. Org. Chem. 1994, 59: 6313Reference Ris Wihthout Link - 83
Mahoney WS.Brestensky DM.Stryker JM. J. Am. Chem. Soc. 1988, 110: 291Reference Ris Wihthout Link - 84
Reusch W.Grimm K.Karoglan JE.Martin J.Subrahamanian KP.Toong Y.Venkataramani PS.Yordy JD.Zoutendam P. J. Am. Chem. Soc. 1977, 99: 1953Reference Ris Wihthout Link - 85
Reusch W.Grimm K.Karoglan JE.Martin J.Subrahamanian KP.Venkataramani PS.Yordy JD.
J. Am. Chem. Soc. 1977, 99: 1958Reference Ris Wihthout Link - 86
Ciceri P.Demnitz FWJ. Tetrahedron Lett. 1997, 38: 389Reference Ris Wihthout Link - 87
Kawabata T.Mizugaki T.Ebitani K.Kaneda K. Tetrahedron Lett. 2001, 42: 8329Reference Ris Wihthout Link - 88
Bauduin G.Pietrasanta Y. Tetrahedron 1973, 29: 4225Reference Ris Wihthout Link - 89
Hwu JR.Wetzel JM. J. Org. Chem. 1985, 50: 3946Reference Ris Wihthout Link - 90
Swaminathan S.Newman MS. Tetrahedron 1958, 2: 88Reference Ris Wihthout Link - 91
Zorn N.Lett R. Tetrahedron Lett. 2006, 47: 4331Reference Ris Wihthout Link - 92
Grieco PA.Ferrino S.Oguri T. J. Org. Chem. 1979, 44: 2593Reference Ris Wihthout Link - 93a For
the synthesis of compounds 73-82 see:
Vellekoop AS.Smith RAJ. Tetrahedron 1998, 54: 11971Reference Ris Wihthout Link - 93b For the synthesis of 83 see:
Lo L.Shie J.Chou T. J. Org. Chem. 2002, 67: 282Reference Ris Wihthout Link - 93c For the synthesis of 84 see:
Enomoto M.Kuwahara S. J. Org. Chem. 2010, 75: 6286Reference Ris Wihthout Link - 93d
For the synthesis of 85 see ref. 24.
Reference Ris Wihthout Link - 94a
Heathcock CH.Ratcliffe R. J. Am. Chem. Soc. 1971, 93: 1746Reference Ris Wihthout Link - 94b
Payette JN.Honda T.Yoshizawa H.Favaloro FG.Gribble GW. J. Org. Chem. 2006, 71: 416Reference Ris Wihthout Link - 95
Newman MS.Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039Reference Ris Wihthout Link - 96
Jones JB.Leman JD.Marr PW. Can. J. Chem. 1971, 49: 1604Reference Ris Wihthout Link - 97a
Zaidi JH.Waring AJ. J. Chem. Soc., Chem. Commun. 1980, 618Reference Ris Wihthout Link - 97b
Waring AJ.Zaidi JH. J. Chem. Soc., Perkin Trans. 1 1985, 631Reference Ris Wihthout Link - 98
Trost BM.Salzmann TN. J. Chem. Soc., Chem. Commun. 1975, 571Reference Ris Wihthout Link - 99a
Bortolini O.Conte V.Chiappe C.Fantin G.Fogagnolo M.Maietti S. Green Chem. 2002, 4: 94Reference Ris Wihthout Link - 99b
Bortolini O.Campestrini S.Conte V.Fantin G.Fogagnolo M.Maietti S. Eur. J. Org. Chem. 2003, 4804Reference Ris Wihthout Link - 100
Molander GA.Hahn G. J. Org. Chem. 1986, 51: 2596Reference Ris Wihthout Link - 101
Zhu R.Xing L.Wang X.Cheng C.Liu B.Hu Y. Synlett 2007, 2267Reference Ris Wihthout Link - 102
Ottolina G.de Gonzalo G.Carrea G.Danieli B. Adv. Synth. Catal. 2005, 347: 1035Reference Ris Wihthout Link - 103
Shimizu T.Hiranuma S.Yoshioka H. Chem. Pharm. Bull. 1989, 37: 1963Reference Ris Wihthout Link - 104
Gopalakrishnan G.Jayaraman S.Rajagopalan K.Swaminathan S. Synthesis 1983, 797Reference Ris Wihthout Link - 105
Chemler SR.Danishefsky SJ. Org. Lett. 2000, 2: 2695Reference Ris Wihthout Link - 106
Newman MS.Ramachandran S.Sankarappa SK.Swaminathan S. J. Org. Chem. 1961, 26: 727Reference Ris Wihthout Link - 107
Curini M.Epifano F.Marcotullio MC.Rosati O.Rossi M. Synlett 1999, 315Reference Ris Wihthout Link - 108
Golinski M.Brock CP.Watt DS. J. Org. Chem. 1993, 58: 159Reference Ris Wihthout Link - 109
Geetha P.Narasimhan K.Swaminathan S. Tetrahedron Lett. 1979, 20: 565Reference Ris Wihthout Link - 110a
Smith RAJ.Hannah DJ. Tetrahedron 1979, 35: 1183Reference Ris Wihthout Link - 110b
Bradshaw B.Etxebarria-Jardi G.Bonjoch J. Org. Biomol. Chem. 2008, 6: 772Reference Ris Wihthout Link - 111
Henze W.Gärtner T.Gschwind RM. J. Am. Chem. Soc. 2008, 130: 13718Reference Ris Wihthout Link - 112
Hanselmann R. Ph.D. Thesis University of Calgary; Canada: 1996. https://dspace.ucalgary.ca/bitstream/880/29331/1/20740Hanselmann.pdfReference Ris Wihthout Link - 113
Hikage N.Furukawa H.Takao K.Kobayashi S. Tetrahedron Lett. 1998, 39: 6237Reference Ris Wihthout Link - 114
Flemming S.Kabbara J.Nickisch K.Neh H.Westermann J. Tetrahedron Lett. 1994, 35: 6075Reference Ris Wihthout Link - 115
Flemming S.Kabbara J.Nickisch K.Neh H.Westermann J. Synthesis 1995, 317Reference Ris Wihthout Link - 116
Hagiwara H.Okamoto T.Harada N.Uda H. Tetrahedron 1995, 51: 9891Reference Ris Wihthout Link - 117
Ling T.Chowdhury C.Kramer BA.Vong BG.Palladino MA.Theodorakis EA. J. Org. Chem. 2001, 66: 8843Reference Ris Wihthout Link - 118
Arséniyadis S.Rodriguez R.Cabrera E.Thompson A.Ourisson G. Tetrahedron 1991, 47: 7045Reference Ris Wihthout Link - 119
Pemp A.Seifert K. Tetrahedron Lett. 1997, 38: 2081Reference Ris Wihthout Link - 120a
Smith AB.Kürti L.Davulcu AH.Cho YS. Org. Process Res. Dev. 2007, 11: 19Reference Ris Wihthout Link - 120b
Lanfranchi DA.Baldovini N.Hanquet G. Synthesis 2008, 3775Reference Ris Wihthout Link - 120c For the original procedure,
see:
Kirk DN.Petrow V. J. Chem. Soc. 1962, 1091Reference Ris Wihthout Link - 121
Churruca F.Fousteris M.Ishikawa Y.von Wantoch Rekowski M.Hounsou C.Surrey T.Giannis A. Org. Lett. 2010, 12: 2096Reference Ris Wihthout Link - 122a
Stork G.Danishefsky S.Ohashi M. J. Am. Chem. Soc. 1967, 89: 5459Reference Ris Wihthout Link - 122b
Stork G.McMurry JE. J. Am. Chem. Soc. 1967, 89: 5464Reference Ris Wihthout Link - 123
Shah N.Scanlan TS. Bioorg. Med. Chem. Lett. 2004, 14: 5199Reference Ris Wihthout Link - 124
Magnus P.Taylor GM. J. Chem. Soc., Perkin Trans. 1 1991, 2657Reference Ris Wihthout Link - 125
Greco CV.Gray RP. Tetrahedron 1970, 26: 4329Reference Ris Wihthout Link - 126
Abbiati G.Arcadi A.Bianchi G.Di Giuseppe S.Marinelli F.Rossi E. J. Org. Chem. 2003, 68: 6959Reference Ris Wihthout Link - 127
Zhang X.Li X.Allan GF.Musto A.Lundeen SG.Sui Z. Bioorg. Med. Chem. Lett. 2006, 16: 3233Reference Ris Wihthout Link - 128
Guerrero A.Parrilla A.Camps F. Tetrahedron Lett. 1990, 31: 1873Reference Ris Wihthout Link - 129 For initial work see also:
Magee TV.Bornmann WG.Isaacs RCA.Danishefsky SJ. J. Org. Chem. 1992, 57: 3274Reference Ris Wihthout Link - 130
Golinski M.Vasudevan S.Floresca R.Brock CP.Watt DS. Tetrahedron Lett. 1993, 34: 55Reference Ris Wihthout Link - 131
Lu Y.Peng X. Org. Lett. 2011, 13: 2940Reference Ris Wihthout Link - 132
Liu H.Siegel DR.Danishefsky SJ. Org. Lett. 2006, 8: 423Reference Ris Wihthout Link - 133
Chanu A.Castellote I.Commeureuc A.Safir I.Arseniyadis S. Tetrahedron: Asymmetry 2006, 17: 2565Reference Ris Wihthout Link
References
Catalysts 16 and 17 were tested in the synthesis of compound 52 (Scheme [9] ) not the WMK itself.
38Furthermore it would seem that the enantioselectivities were measured directly from the reaction mixture not the purified compounds. Since prolinamide intermediates were formed in the reaction mixture it may well be that kinetic resolution led to an increase in one enantiomer. The observation that the related catalyst 17, screened by Zhang gave a consid-erably reduced enantioselectivity would seem to support this hypothesis.
61Bradshaw, B.; Bonjoch, J. unpublished work.
65This catalyst was first introduced by the Najera group (see ref. 33) and with whom the methodological part of this work was developed in collaboration.