The Wieland-Miescher
Ketone: A Journey from Organocatalysis to Natural Product Synthesis

Ben Bradshaw; Josep Bonjoch

doi:10.1055/s-0031-1290107

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2012(3): 337-356
DOI: 10.1055/s-0031-1290107

ACCOUNT

The Wieland-Miescher Ketone: A Journey from Organocatalysis to Natural Product Synthesis

Ben Bradshaw*, Josep Bonjoch*
Laboratori de Química Orgànica, Facultat de Farmàcia, Universitat de Barcelona, IBUB, Av. Joan XXIII s/n, 08028 Barcelona, Spain
Fax: +34(934)024539; e-Mail: benbradshaw@ub.edu, josep.bonjoch@ub.edu;

Further Information

Publication History

Received 13 July 2011
Publication Date:
09 December 2011 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

References

1 List B. Lerner RA. Barbas CF. J. Am. Chem. Soc. 2000, 122: 2395

Google Scholar
2 Ahrendt KA. Borths CJ. MacMillan DWC. J. Am. Chem. Soc. 2000, 122: 4243

Google Scholar
3 Bertelsen S. Jørgensen KA. Chem. Soc. Rev. 2009, 38: 2178

Google Scholar
4a Hajos ZG, and Parrish DR. inventors; DE 2102623.
4b Eder U, Sauer GR, and Wiechert R. inventors; DE 2014757.
4c Eder U. Sauer GR. Wiechert R. Angew. Chem., Int. Ed. Engl. 1971, 10: 496 ; Angew. Chem. 1971, 83, 492

Google Scholar
4d Hajos ZG. Parrish DR. J. Org. Chem. 1974, 39: 1615

Google Scholar
5 MacMillan DWC. Nature 2008, 455: 304

Google Scholar
6 Barbas CF. Angew. Chem. Int. Ed. 2008, 47: 42

Google Scholar
7a Corey EJ. Ohno M. Vatakencherry PA. Mitra RB. J. Am. Chem. Soc. 1961, 83: 1251

Google Scholar
7b Corey EJ. Ohno M. Mitra RB. Vatakencherry PA. J. Am. Chem. Soc. 1964, 86: 478

Google Scholar
7c Piers E. Britton RW. De Waal W. J. Chem. Soc. D 1969, 1069

Google Scholar
7d Piers E. De Waal W. Britton RW. J. Am. Chem. Soc. 1971, 93: 5113

Google Scholar
7e Heathcock CH. DelMar EG. Graham SL. J. Am. Chem. Soc. 1982, 104: 1907

Google Scholar
7f Smith AB. Mewshaw R. J. Org. Chem. 1984, 49: 3685

Google Scholar
7g Shishido K. Tokunaga Y. Omachi N. Hiroya K. Fukumoto K. Kametani T.
J. Chem. Soc., Chem. Commun. 1989, 1093

Google Scholar
7h Smith AB. Sunazuka T. Leenay TL. Kingery-Wood J. J. Am. Chem. Soc. 1990, 112: 8197

Google Scholar
7i Smith AB. Kingery-Wood J. Leenay TL. Nolen EG. Sunazuka T. J. Am. Chem. Soc. 1992, 114: 1438

Google Scholar
7j Grieco PA. Collins JL. Moher ED. Fleck TJ. Gross RS. J. Am. Chem. Soc. 1993, 115: 6078

Google Scholar
7k Paquette LA. Wang T. Philippo CMG. Wang S. J. Am. Chem. Soc. 1994, 116: 3367

Google Scholar
7l Ziegler FE. Wallace OB. J. Org. Chem. 1995, 60: 3626

Google Scholar
7m Dzierba CD. Zandi KS. Möllers T. Shea KJ. J. Am. Chem. Soc. 1996, 118: 4711

Google Scholar
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: 2843

Google Scholar
7o Stork G. West F. Lee HY. Isaacs RCA. Manabe S. J. Am. Chem. Soc. 1996, 118: 10660

Google Scholar
7p An J. Wiemer DF. J. Org. Chem. 1996, 61: 8775

Google Scholar
7q Paquette LA. Backhaus D. Braun R. Underiner TL. Fuchs K. J. Am. Chem. Soc. 1997, 119: 9662

Google Scholar
7r Harada N. Sugioka T. Ando Y. Uda H. Kuriki T. J. Am. Chem. Soc. 1988, 110: 8483

Google Scholar
7s Kurosu M. Marcin LR. Grinsteiner TJ. Kishi Y. J. Am. Chem. Soc. 1998, 120: 6627

Google Scholar
7t Karimi S. Tavares P. J. Nat. Prod. 2003, 66: 520

Google Scholar
7u Kende AS. Deng W. Zhong M. Guo X. Org. Lett. 2003, 5: 1785

Google Scholar
7v Deng W. Zhong M. Guo X. Kende AS. J. Org. Chem. 2003, 68: 7422

Google Scholar
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: 8228

Google Scholar
7x Waters SP. Tian Y. Li Y. Danishefsky SJ. J. Am. Chem. Soc. 2005, 127: 13514

Google Scholar
7y Díaz S. González A. Bradshaw B. Cuesta J. Bonjoch J. J. Org. Chem. 2005, 70: 3749

Google Scholar
7z Peng X. Wong HNC. Chem. Asian J. 2006, 1: 111

Google Scholar
(aa) Ferraz HMC. Souza AJC. Tenius BSM. Bianco GG. Tetrahedron 2006, 62: 9232

Google Scholar
(ab) Chanu A. Safir I. Basak R. Chiaroni A. Arseniyadis S. Org. Lett. 2007, 9: 1351

Google Scholar
(ac) Hanessian S. Boyer N. Reddy GJ. Deschênes-Simard B. Org. Lett. 2009, 11: 4640

Google Scholar
(ad) Carneiro VMT. Ferraz HMC. Vieira TO. Ishikawa EE. Silva LF. J. Org. Chem. 2010, 75: 2877

Google Scholar
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: 1746

Google Scholar
8b longifolene: McMurry JE. Isser SJ. J. Am. Chem. Soc. 1972, 94: 7132

Google Scholar
8c muzigadial: Bosch MP. Camps F. Coll J. Guerrero A. Tatsuoka T. Meinwald J. J. Org. Chem. 1986, 51: 773

Google Scholar
8d paspaline: Mewshaw RE. Taylor MD. Smith AB. J. Org. Chem. 1989, 54: 3449

Google Scholar
8e phytocassane D: Yajima A. Mori K. Eur. J. Org. Chem. 2000, 4079

Google Scholar
8f longifolene: Karimi S. Tavares P. J. Nat. Prod. 2003, 66: 520

Google Scholar
8g 21-isopentenylpaxilline: Smith AB. Cui H. Org. Lett. 2003, 5: 587

Google Scholar
8h nodulisporic acid F: Smith AB. Davulcu AH. Kürti L. Org. Lett. 2006, 8: 1665

Google Scholar
8i integric acid: Waalboer DCJ. van Kalkeren HA. Schaapman MC. van Delft FL. Rutjes FPJT. J. Org. Chem. 2009, 74: 8878

Google Scholar
8j carainterol A: Ma K. Zhang C. Liu M. Chu Y. Zhou L. Hu C. Ye D. Tetrahedron Lett. 2010, 51: 1870

Google Scholar
9 For a detailed overview see: Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev. 2007, 107: 5471

Google Scholar
10 Wieland P. Miescher K. Helv. Chim. Acta 1950, 33: 2215

Google Scholar
For other racemic approaches to the Wieland-Miescher ketone see
11a Wendler NL. Slates HL. Tishler M.
J. Am. Chem. Soc. 1951, 73: 3816

Google Scholar
11b Sondheimer F. Elad D. J. Am. Chem. Soc. 1957, 79: 5542

Google Scholar
11c Swaminathan S. Newman MS. Tetrahedron 1958, 2: 88

Google Scholar
11d Newman MS. Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039

Google Scholar
11e Newman MS. Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039

Google Scholar
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, 56

Google Scholar
11g Sondheimer F. Elad D.
J. Am. Chem. Soc. 1957, 79: 5542

Google Scholar
12a Bahmanyar S. Houk KN. J. Am. Chem. Soc. 2001, 123: 11273

Google Scholar
12b Bahmanyar S. Houk KN. Martin HJ. List B. J. Am. Chem. Soc. 2003, 125: 2475

Google Scholar
13a Stork G. Brizzolara A. Landesman H. Szmuszkovicz J. Terrell R. J. Am. Chem. Soc. 1963, 85: 207

Google Scholar
13b Stork G. Saccomano NA. Tetrahedron Lett. 1987, 28: 2087

Google Scholar
13c The Chemistry of Enamines Rappoport Z. Wiley; New York: 1994.

Google Scholar
14 Machajewski TD. Wong C.-H. Angew. Chem. Int. Ed. 2000, 39: 1352

Google Scholar
15 Jung ME. Tetrahedron 1976, 32: 3

Google Scholar
16 List B. Hoang L. Martin HJ. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 5839

Google Scholar
17a Puchot C. Samuel O. Dunach E. Zhao S. Agami C. Kagan HB. J. Am. Chem. Soc. 1986, 108: 2353

Google Scholar
17b Agami C. Meynier F. Puchot C. Guilhem J. Pascard C. Tetrahedron 1984, 40: 1031

Google Scholar
18 Hoang L. Bahmanyar S. Houk KN. List B. J. Am. Chem. Soc. 2003, 125: 16

Google Scholar
19 Rajagopal D. Moni MS. Subramanian S. Swaminathan S. Tetrahedron: Asymmetry 1999, 10: 1631

Google Scholar
20a Bui T. Barbas CF. Tetrahedron Lett. 2000, 41: 6951

Google Scholar
For a modified approach using MeCN as the solvent see:
20b Lazarski KE. Rich AA. Mascarenhas CM.
J. Chem. Educ. 2008, 85: 1531

Google Scholar
21 Gutzwiller J. Buchschacher P. Fürst A. Synthesis 1977, 167

Google Scholar
22 Buchschacher P. Fürst A. Org. Synth. 1985, 63: 3743

Google Scholar
23 Harada N. Sugioka T. Uda H. Kuriki T. Synthesis 1990, 53

Google Scholar
24 Tietze LF. Utecht J. Synthesis 1993, 957

Google Scholar
25a Hioki H. Hashimoto T. Kodama M. Tetrahedron: Asymmetry 2000, 11: 829

Google Scholar
25b Fuhshuku K. Funa N. Akeboshi T. Ohta H. Hosomi H. Ohba S. Sugai T.
J. Org. Chem. 2000, 65: 129

Google Scholar
25c Fuhshuku K. Tomita M. Sugai T. Adv. Synth. Catal. 2003, 345: 766

Google Scholar
26 Kasai Y. Shimanuki K. Kuwahara S. Watanabe M. Harada N. Chirality 2006, 18: 177

Google Scholar
27 Zhong G. Hoffmann T. Lerner RA. Danishefsky S. Barbas CF. J. Am. Chem. Soc. 1997, 119: 8131

Google Scholar
28a Davies SG. Sheppard RL. Smith AD. Thomson JE. Chem. Commun. 2005, 3802

Google Scholar
28b Davies SG. Russell AJ. Sheppard RL. Smith AD. Thomson JE. Org. Biomol. Chem. 2007, 5: 3190

Google Scholar
29 Lacoste E. Vaique E. Berlande M. Pianet I. Vincent J. Landais Y. Eur. J. Org. Chem. 2007, 167

Google Scholar
30a Akahane Y. Inage N. Nagamine T. Inomata K. Endo Y. Heterocycles 2007, 74: 637

Google Scholar
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.
31a Kanger T. Kriis K. Laars M. Kailas T. Müürisepp A. Pehk T. Lopp M. J. Org. Chem. 2007, 72: 5168

Google Scholar
31b Laars M. Kriis K. Kailas T. Müürisepp A. Pehk T. Kanger T. Lopp M. Tetrahedron: Asymmetry 2008, 19: 641

Google Scholar
32 D’Elia V. Zwicknagl H. Reiser O. J. Org. Chem. 2008, 73: 3262

Google Scholar
33 Guillena G. Nájera C. Viózquez SF. Synlett 2008, 3031

Google Scholar
34 Almaºi D. Alonso DA. Nájera C. Adv. Synth. Catal. 2008, 350: 2467

Google Scholar
36 Zhang X. Wang M. Tu Y. Fan C. Jiang Y. Zhang S. Zhang F. Synlett 2008, 2831

Google Scholar
37 Fuentes de Arriba L. Simón L. Raposo C. Alcázar V. Morán JR. Tetrahedron 2009, 65: 4841

Google Scholar
39a Akahane Y. Inomata K. Endo Y. Heterocycles 2009, 77: 1065

Google Scholar
39b Akahane Y. Inomata K. Endo Y. Heterocycles 2011, 82: 1727

Google Scholar
40 Fuentes de Arriba L. Seisdedos DG. Simón L. Alcázar V. Raposo C. Morán JR. J. Org. Chem. 2010, 75: 8303

Google Scholar
41 Díaz S. Cuesta J. González A. Bonjoch J. J. Org. Chem. 2003, 68: 7400

Google Scholar
42 Gloer JB. Rinderknecht BL. Wicklow DT. Dowd PF. J. Org. Chem. 1989, 54: 2530

Google Scholar
43 TePaske MR. Gloer JB. Wicklow DT. Dowd PF. J. Org. Chem. 1989, 54: 4743

Google Scholar
44 Gloer JB. TePaske MR. Sima JS. Wicklow DT. Dowd PF. J. Org. Chem. 1988, 53: 5457

Google Scholar
45 Staub GM. Gloer JB. Wicklow DT. Dowd PF.
J. Am. Chem. Soc. 1992, 114: 1015

Google Scholar
46 For an approach to aflavinine 24 see: Danishefsky S. Chackalamannil S. Harrison P. Silvestri M. Cole P.
J. Am. Chem. Soc. 1985, 107: 2474

Google Scholar
47a Liu Y. McWhorter WW. Hadden CE. Org. Lett. 2003, 5: 333

Google Scholar
47b Ho GA. Nouri DH. Tantillo DJ. Tetrahedron Lett. 2009, 50: 1578

Google Scholar
47c Marcos IS. Moro RF. Costales I. Escola MA. Basabe P. Díez D. Urones JG. Tetrahedron 2009, 65: 10235

Google Scholar
48a Crow WD. Aust. J. Chem. 1962, 15: 159

Google Scholar
48b Fridrichsons J. Mathieson AMcL. Tetrahedron Lett. 1960, 1: 18

Google Scholar
48c Fridrichsons J. Mathieson AMcL. Acta Crystallogr. 1963, 16: 206

Google Scholar
49 Iwagawa T. Kaneko M. Okamura H. Nakatani M. van Soest RWM. J. Nat. Prod. 1998, 61: 1310

Google Scholar
50 Johnson TA. Amagata T. Sashidhara KV. Oliver AG. Tenney K. Matainaho T. Ang KK. McKerrow JH. Crews P. Org. Lett. 2009, 11: 1975

Google Scholar
51 Díaz S. González A. Bradshaw B. Cuesta J. Bonjoch J. J. Org. Chem. 2005, 70: 3749

Google Scholar
52 For other examples of the difficulty of 1,4 addition to the WMK 1 see: Streuff J. Chem.-Eur. J. 2011, 17: 5507

Google Scholar
53 Lipshutz BH. Ellsworth EL. J. Am. Chem. Soc. 1990, 112: 7440

Google Scholar
54a Kwiatkowski S. Syed A. Brock CP. Watt DS. Synthesis 1989, 818

Google Scholar
54b Hanselmann R. Benn M. Synth. Commun. 1996, 26: 945

Google Scholar
For an alternative synthesis of the allyl WMK analogue see:
54c Hiroya K. Takahashi T. Shimomae K. Sakamoto T. Chem. Pharm. Bull. 2005, 53: 207

Google Scholar
54d Inomata K. Barragué M. Paquette LA. J. Org. Chem. 2005, 70: 533

Google Scholar
54e Ramachary DB. Kishor M.
J. Org. Chem. 2007, 72: 5056

Google Scholar
For examples of WMK analogues in total synthesis see:
55a
ref. 7l.

Google Scholar
55b Hamilton RJ. Mander LN. Sethi SP. Tetrahedron 1986, 42: 2881

Google Scholar
55c Nicolaou KC. Roecker AJ. Monenschein H. Guntupalli P. Follmann M. Angew. Chem. Int. Ed. 2003, 42: 3637

Google Scholar
56 Prakash C. Mohanakrishnan AK. Eur. J. Org. Chem. 2008, 1535

Google Scholar
57 Rajamannar T. Palani N. Balasubramanian K. Synth. Commun. 1993, 23: 3095

Google Scholar
58 Inomata K. Barragué M. Paquette LA. J. Org. Chem. 2005, 70: 533

Google Scholar
59 Kennedy JWJ. Vietrich S. Weinmann H. Brittain DEA. J. Org. Chem. 2008, 73: 5151

Google Scholar
60 Piers E. Grierson JR. J. Org. Chem. 1977, 42: 3755

Google Scholar
62 Birch AJ. J. Chem. Soc. 1947, 102

Google Scholar
63 Vidari G. Lanfranchi G. Masciaga F. Moriggi J. Tetrahedron: Asymmetry 1996, 7: 3009

Google Scholar
64 Bradshaw B. Etxebarría-Jardi G. Bonjoch J. Viózquez S. Guillena G. Nájera C. Adv. Synth. Catal. 2009, 351: 2482

Google Scholar
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: 2189

Google Scholar
67 Viózquez S. Guillena G. Nájera C. Bradshaw B. Etxebarría-Jardi G. Bonjoch J. Org. Synth. 2011, 88: 317

Google Scholar
68 Etxebarria-Jardí G. Ph.D Thesis University of Barcelona; Spain: 2010.

Google Scholar
69 Bradshaw B. Etxebarria-Jardí G. Bonjoch J. J. Am. Chem. Soc. 2010, 132: 5966

Google Scholar
70 Bradshaw B. Etxebarría-Jardi G. Bonjoch J. Viózquez S. Guillena G. Nájera C. Org. Synth. 2011, 88: 330

Google Scholar
71 Walji AM. MacMillan DWC. Synlett 2007, 1477

Google Scholar
72 Ward DE. Rhee CK. Zoghaib WM. Tetrahedron Lett. 1988, 29: 517

Google Scholar
73 Sarkar DC. Das AR. Ranu BC. J. Org. Chem. 1990, 55: 5799

Google Scholar
74 Midland MM. McLoughlin JI. Gabriel J. J. Org. Chem. 1989, 54: 159

Google Scholar
75 Andrews GC. Crawford TC. Tetrahedron Lett. 1980, 21: 693

Google Scholar
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: 12073

Google Scholar
77 Van Gool M. Vandewalle M. Eur. J. Org. Chem. 2000, 3427

Google Scholar
78 Banerjee A. Poon PS. Laya M. Synth. Commun. 2003, 33: 1929

Google Scholar
79 Ramachary DB. Sakthidevi R. Org. Biomol. Chem. 2008, 6: 2488

Google Scholar
80 Ito H. Ishizuka T. Arimoto K. Miura K. Hosomi A. Tetrahedron Lett. 1997, 38: 8887

Google Scholar
81 von Holleben MLA. Zucolotto M. Zini CA. Oliveira ER. Tetrahedron 1994, 50: 973

Google Scholar
82 Park K. Scott WJ. Wiemer DF. J. Org. Chem. 1994, 59: 6313

Google Scholar
83 Mahoney WS. Brestensky DM. Stryker JM. J. Am. Chem. Soc. 1988, 110: 291

Google Scholar
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: 1953

Google Scholar
85 Reusch W. Grimm K. Karoglan JE. Martin J. Subrahamanian KP. Venkataramani PS. Yordy JD.
J. Am. Chem. Soc. 1977, 99: 1958

Google Scholar
86 Ciceri P. Demnitz FWJ. Tetrahedron Lett. 1997, 38: 389

Google Scholar
87 Kawabata T. Mizugaki T. Ebitani K. Kaneda K. Tetrahedron Lett. 2001, 42: 8329

Google Scholar
88 Bauduin G. Pietrasanta Y. Tetrahedron 1973, 29: 4225

Google Scholar
89 Hwu JR. Wetzel JM. J. Org. Chem. 1985, 50: 3946

Google Scholar
90 Swaminathan S. Newman MS. Tetrahedron 1958, 2: 88

Google Scholar
91 Zorn N. Lett R. Tetrahedron Lett. 2006, 47: 4331

Google Scholar
92 Grieco PA. Ferrino S. Oguri T. J. Org. Chem. 1979, 44: 2593

Google Scholar
93a For the synthesis of compounds 73-82 see: Vellekoop AS. Smith RAJ. Tetrahedron 1998, 54: 11971

Google Scholar
93b For the synthesis of 83 see: Lo L. Shie J. Chou T. J. Org. Chem. 2002, 67: 282

Google Scholar
93c For the synthesis of 84 see: Enomoto M. Kuwahara S. J. Org. Chem. 2010, 75: 6286

Google Scholar
93d
For the synthesis of 85 see ref. 24.
94a Heathcock CH. Ratcliffe R. J. Am. Chem. Soc. 1971, 93: 1746

Google Scholar
94b Payette JN. Honda T. Yoshizawa H. Favaloro FG. Gribble GW. J. Org. Chem. 2006, 71: 416

Google Scholar
95 Newman MS. Mekler AB. J. Am. Chem. Soc. 1960, 82: 4039

Google Scholar
96 Jones JB. Leman JD. Marr PW. Can. J. Chem. 1971, 49: 1604

Google Scholar
97a Zaidi JH. Waring AJ. J. Chem. Soc., Chem. Commun. 1980, 618

Google Scholar
97b Waring AJ. Zaidi JH. J. Chem. Soc., Perkin Trans. 1 1985, 631

Google Scholar
98 Trost BM. Salzmann TN. J. Chem. Soc., Chem. Commun. 1975, 571

Google Scholar
99a Bortolini O. Conte V. Chiappe C. Fantin G. Fogagnolo M. Maietti S. Green Chem. 2002, 4: 94

Google Scholar
99b Bortolini O. Campestrini S. Conte V. Fantin G. Fogagnolo M. Maietti S. Eur. J. Org. Chem. 2003, 4804

Google Scholar
100 Molander GA. Hahn G. J. Org. Chem. 1986, 51: 2596

Google Scholar
101 Zhu R. Xing L. Wang X. Cheng C. Liu B. Hu Y. Synlett 2007, 2267

Google Scholar
102 Ottolina G. de Gonzalo G. Carrea G. Danieli B. Adv. Synth. Catal. 2005, 347: 1035

Google Scholar
103 Shimizu T. Hiranuma S. Yoshioka H. Chem. Pharm. Bull. 1989, 37: 1963

Google Scholar
104 Gopalakrishnan G. Jayaraman S. Rajagopalan K. Swaminathan S. Synthesis 1983, 797

Google Scholar
105 Chemler SR. Danishefsky SJ. Org. Lett. 2000, 2: 2695

Google Scholar
106 Newman MS. Ramachandran S. Sankarappa SK. Swaminathan S. J. Org. Chem. 1961, 26: 727

Google Scholar
107 Curini M. Epifano F. Marcotullio MC. Rosati O. Rossi M. Synlett 1999, 315

Google Scholar
108 Golinski M. Brock CP. Watt DS. J. Org. Chem. 1993, 58: 159

Google Scholar
109 Geetha P. Narasimhan K. Swaminathan S. Tetrahedron Lett. 1979, 20: 565

Google Scholar
110a Smith RAJ. Hannah DJ. Tetrahedron 1979, 35: 1183

Google Scholar
110b Bradshaw B. Etxebarria-Jardi G. Bonjoch J. Org. Biomol. Chem. 2008, 6: 772

Google Scholar
111 Henze W. Gärtner T. Gschwind RM. J. Am. Chem. Soc. 2008, 130: 13718

Google Scholar
112 Hanselmann R. Ph.D. Thesis University of Calgary; Canada: 1996. https://dspace.ucalgary.ca/bitstream/880/29331/1/20740Hanselmann.pdf

Google Scholar
113 Hikage N. Furukawa H. Takao K. Kobayashi S. Tetrahedron Lett. 1998, 39: 6237

Google Scholar
114 Flemming S. Kabbara J. Nickisch K. Neh H. Westermann J. Tetrahedron Lett. 1994, 35: 6075

Google Scholar
115 Flemming S. Kabbara J. Nickisch K. Neh H. Westermann J. Synthesis 1995, 317

Google Scholar
116 Hagiwara H. Okamoto T. Harada N. Uda H. Tetrahedron 1995, 51: 9891

Google Scholar
117 Ling T. Chowdhury C. Kramer BA. Vong BG. Palladino MA. Theodorakis EA. J. Org. Chem. 2001, 66: 8843

Google Scholar
118 Arséniyadis S. Rodriguez R. Cabrera E. Thompson A. Ourisson G. Tetrahedron 1991, 47: 7045

Google Scholar
119 Pemp A. Seifert K. Tetrahedron Lett. 1997, 38: 2081

Google Scholar
120a Smith AB. Kürti L. Davulcu AH. Cho YS. Org. Process Res. Dev. 2007, 11: 19

Google Scholar
120b Lanfranchi DA. Baldovini N. Hanquet G. Synthesis 2008, 3775

Google Scholar
120c For the original procedure, see: Kirk DN. Petrow V. J. Chem. Soc. 1962, 1091

Google Scholar
121 Churruca F. Fousteris M. Ishikawa Y. von Wantoch Rekowski M. Hounsou C. Surrey T. Giannis A. Org. Lett. 2010, 12: 2096

Google Scholar
122a Stork G. Danishefsky S. Ohashi M. J. Am. Chem. Soc. 1967, 89: 5459

Google Scholar
122b Stork G. McMurry JE. J. Am. Chem. Soc. 1967, 89: 5464

Google Scholar
123 Shah N. Scanlan TS. Bioorg. Med. Chem. Lett. 2004, 14: 5199

Google Scholar
124 Magnus P. Taylor GM. J. Chem. Soc., Perkin Trans. 1 1991, 2657

Google Scholar
125 Greco CV. Gray RP. Tetrahedron 1970, 26: 4329

Google Scholar
126 Abbiati G. Arcadi A. Bianchi G. Di Giuseppe S. Marinelli F. Rossi E. J. Org. Chem. 2003, 68: 6959

Google Scholar
127 Zhang X. Li X. Allan GF. Musto A. Lundeen SG. Sui Z. Bioorg. Med. Chem. Lett. 2006, 16: 3233

Google Scholar
128 Guerrero A. Parrilla A. Camps F. Tetrahedron Lett. 1990, 31: 1873

Google Scholar
129 For initial work see also: Magee TV. Bornmann WG. Isaacs RCA. Danishefsky SJ. J. Org. Chem. 1992, 57: 3274

Google Scholar
130 Golinski M. Vasudevan S. Floresca R. Brock CP. Watt DS. Tetrahedron Lett. 1993, 34: 55

Google Scholar
131 Lu Y. Peng X. Org. Lett. 2011, 13: 2940

Google Scholar
132 Liu H. Siegel DR. Danishefsky SJ. Org. Lett. 2006, 8: 423

Google Scholar
133 Chanu A. Castellote I. Commeureuc A. Safir I. Arseniyadis S. Tetrahedron: Asymmetry 2006, 17: 2565

Google Scholar

35

Catalysts 16 and 17 were tested in the synthesis of compound 52 (Scheme [9] ) not the WMK itself.

38

Furthermore 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.

61

Bradshaw, B.; Bonjoch, J. unpublished work.

65

This catalyst was first introduced by the Najera group (see ref. 33) and with whom the methodological part of this work was developed in collaboration.