Directed ortho Metalation (DoM)-Linked Corriu–Kumada, Negishi, and Suzuki–Miyaura Cross-Coupling Protocols: A Comparative Study

Claude A. Quesnelle; Victor Snieckus

doi:10.1055/s-0037-1611053

Synthesis, Table of Contents

Synthesis 2018; 50(22): 4395-4412
DOI: 10.1055/s-0037-1611053

paper

Directed ortho Metalation (DoM)-Linked Corriu–Kumada, Negishi, and Suzuki–Miyaura Cross-Coupling Protocols: A Comparative Study

Claude A. Quesnelle

,

Victor Snieckus*

Abstract

All articles of this category

Dedicated to Scott Denmark: By this, we (and KB in absentia) are celebrating your creativity and stellar achievements.

Published as part of the Special Section dedicated to Scott E. Denmark on the occasion of his 65^th birthday.

Abstract

A systematic study of the widely used, titled name reaction transition-metal-catalyzed cross-coupling reactions with attention to context with the directed ortho metalation (DoM) is reported. In general, the Suzuki–Miyaura and Negishi protocols show greater scope and better yields than the Corriu–Kumada variant, although the latter qualitatively proceeds at fastest rate but has low functional group tolerance. The Negishi process is shown to be useful for substrates with nucleophile and base-sensitive functionality and it is comparable to the Suzuki–Miyaura reaction in efficiency. The link of these cross-coupling reactions to the DoM strategy lends itself to the regioselective construction of diversely substituted aromatics and heteroaromatics.

Key words

Suzuki–Miyaura coupling - Negishi coupling - Kumada coupling - comparison

Full Text

References

References
1 Current Address: Bristol-Myers Squibb Co., Department of Medicinal Chemistry, Princeton, NJ 08543-4000, USA.

2a de Meijere A, Brase S, Oestreich M. Metal-Catalyzed Cross-Coupling Reactions and More . Vols 1-3. Wiley-VCH; Weinheim: 2014
2b For a chronologically historical conceptual perspective with original and leading references, see: Johansson Seechurn CC. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
2c See also: Roy D, Uozumi Y. Adv. Synth. Catal. 2018; 360: 602

3 Corriu RJ. P, Masse JP. J. Chem. Soc., Chem. Commun. 1972; 144
4 Tamao K, Sumitani K, Kumada M. J. Am. Chem. Soc. 1972; 94: 4374
5 Negishi E.-i, King AO, Okukado N. J. Org. Chem. 1977; 42: 1821

6a Kosugi M, Sasazawa K, Shimizu Y, Migita T. Chem. Lett. 1977; 301
6b Milstein D, Stille JK. J. Am. Chem. Soc. 1979; 101: 4992

7a Miyaura N, Yamada K, Suzuki A. Tetrahedron Lett. 1979; 3437
7b Yanagi T, Miyaura N, Suzuki A. Synth. Commun. 1981; 11: 513

8a Hatanaka Y, Hiyama T. Synlett 1991; 845
8b Denmark SE, Regens CS. Acc. Chem. Res. 2008; 41: 1486

9 Sonogashira K, Tohda Y, Hagihara N. Tetrahedron Lett. 1975; 4467
10 The Mizoroki–Heck Reaction . Oestreich M. Wiley; Weinheim: 2009
11 Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
12 King AO, Yasuda N. Top. Organomet. Chem. 2004; 6: 205

13a For an analysis of cross-coupling reactions in the context of a medicinal chemist’s toolbox based on limited set of journals, see: Roughley SD, Jordan AM. J. Med. Chem. 2011; 54: 3451
13b For the development of nanomole-scale high-throughput cross-coupling chemistry for the synthesis of complex molecules, see: Santanilla AB, Regalado EL, Pereira T, Shevlin M, Bateman K, Campeau L.-C, Schneeweis J, Berritt S, Shi Z.-C, Nantermet P, Liu Y, Helmy R, Welch CJ, Vachal P, Davies IW, Cernak T, Dreher SD. Science 2015; 347: 49
13c Recently, Buchwald summarized applications of C–N couplings, see: Ruiz-Castillo P, Buchwald SL. Chem. Rev. 2016; 19: 12564
13d An analysis of the Suzuki–Miyaura coupling for the synthesis of pharmaceutically important heterocycles can be seen here: Almond-Thynne J, Blakemore DC, Pryde DC, Spivey AC. Chem. Sci. 2017; 8: 40

See, for example:

14a Koch FP, Heeney M. In Materials Science and Technology . Cahn RW, Haasen P, Kramer EJ. Wiley-VCH; New York: 2013
14b Xu S, Kim EH, Wei A, Negishi E.-i. Sci. Technol. Adv. Mater. 2014; 15: 1

15a Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
15b For general synthetic and mechanism aspects of C–H activation, see: Tan PW, Haughey M, Dixon DJ. Chem. Commun. 2015; 4406 ; and references to general synthetic and mechanism aspects of C–H activation

For application in the pharmaceutical industry, on small- and large-scale, see for example:

16a Linghu X, Wong N, Jost V, Fantasia S, Sowell CG, Gosselin F. Org. Process Res. Dev. 2017; 21: 1320
16b Znidar D, Hone CA, Inglesby P, Boyd A, Kappe CO. Org. Process Res. Dev. 2017; 21: 878
16c Greshock TJ, Moore KP, McClain RT, Bellomo A, Chung CK, Dreher SD, Kutchukian PS, Peng Z, Davies IW, Vachal P, Ellwart M, Manolikakes SM, Knochel P, Nantermet PG. Angew. Chem. Int. Ed. 2016; 55: 13714
16d Gontcharov A, Dunetz JR. Org. Process Res. Dev. 2014; 18: 1145

See in particular a review outlining many more:

16e Biajoli AF. P, Schwalm CS, Limberger J, Claudino TS, Monteiro AL. J. Braz. Chem. Soc. 2014; 25: 2186
16f See also ref. 13d.

17 Snieckus V. Chem. Rev. 1990; 90: 879
18 Hartung CG, Snieckus V. In Modern Arene Chemistry . Astruc D. Wiley-VCH; New York: 2002: 330
19 Macklin T, Snieckus V. In Handbook of C–H Transformations . Dyker G. Wiley-VCH; New York: 2005: 106
20 For a review on the synthesis of pharmaceuticals, see: Board J, Cosman JL, Rantanen T, Singh S, Snieckus V. Platinum Met. Rev. 2013; 57: 234
21 For phosphinimide DMG – Suzuki–Miyaura coupling, see: Casimiro M, Guedes GP, Iglesias MJ, López Ortiz F. Tetrahedron: Asymmetry 2015; 26: 53

22a Quesnelle CA, Familoni OB, Snieckus V. Synlett 1994; 349
22b Sengupta S, Leite M, Raslan DS, Quesnelle C, Snieckus V. J. Org. Chem. 1992; 57: 4066

23a Macklin TK, Snieckus V. Org. Lett. 2005; 7: 2519
23b See also: Melvin PR, Hazari N, Beromi MM, Shah HP, Williams MJ. Org. Lett. 2016; 18: 5784

24a Antoft-Finch A, Blackburn T, Snieckus V. J. Am. Chem. Soc. 2009; 131: 17750
24b Quasdorf KW, Antoft-Finch A, Liu P, Silberstein AL, Komaromi A, Blackburn T, Ramgren SD, Houk KN, Snieckus V, Garg NK. J. Am. Chem. Soc. 2011; 133: 6352

25a Bumagin NA, Ponomaryov AB, Beletskaya IP. J. Organomet. Chem. 1985; 291: 129
25b See also: Anastasia L, Negishi E.-i. In Handbook of Organopalladium Chemistry for Organic Synthesis. Vol. 1, Negishi E.-i. Wiley-VCH; New York: 2002

26 Although we have studied Stille and Hiyama–Denmark reactions, we have at this stage insufficient data for making generalized observations

To our knowledge, such a comparison has not appeared in the literature. For single cases of comparison, see:

27a Negishi–Suzuki–Miyaura reaction: Brandao MA. F, de Oliveira AB, Snieckus V. Tetrahedron Lett. 1993; 2437
27b Hiyama–Denmark reaction: Mowery ME, DeShong P. J. Org. Chem. 1999; 64: 1684
27c For analogous comparisons of Negishi, Stille, and Sonogashira reactions, see ref. 5.
27d Copenhagen, J. unpublished results.

28 For a previous study, see: Fu J.-m, Snieckus V. Tetrahedron Lett. 1990; 31, 1665

Aside from our work (see references 22, 23, 24), methodological DoM-cross-coupling tactic studies are rare in the non-patent literature; see for example:

29a Bair JS, Palchaudhuri R, Hergenrother PJ. J. Am. Chem. Soc. 2010; 132: 5469
29b Ref. 39a.

30 Chemla F, Ferreira F, Perez-Luna A, Micouin L, Jackowski O. In, Metal-Catalyzed Cross-Coupling Reactions and More . Vol 1. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 365
31 Xu S, Kamada H, Kim EH, Oda A, Negishi E.-i. In, Metal-Catalyzed Cross-Coupling Reactions and More . Vol 1. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 133
32 Martin-Matute B, Szabo KJ, Mitchell TN. In, Metal-Catalyzed Cross-Coupling Reactions and More . Vol 1. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 423
33 Lee JC. H, Hall DG. In, Metal-Catalyzed Cross-Coupling Reactions and More . Vol 1. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 65
34 Dieter MP. Environ. Health Perspect. 1994; 102: 93
35 Denmark SE, Sweis RF. In Metal-Catalyzed Cross-Coupling Reactions and More . Vol 2. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 475

36a Wickham PP, Hazen KH, Guo H, Jones G, Hardee Reuter K, Scott WJ. J. Org. Chem. 1991; 56: 2045
36b Zamiraei Z. Chem. Biol. Interface 2017; 7: 217
36c See also: Snieckus V. Beilstein J. Org. Chem. 2011; 7: 1215

37 For the significance of the heterogeneous state in Pd-catalyzed cross-coupling, see: Biffis A, Centomo P, Del Zotto A, Zecca M. Chem. Rev. 2018; 118: 2249

38a See, for example: Siddiqui MA, Snieckus V. Tetrahedron Lett. 1988; 29: 5463

For recent and alternate syntheses of phenanthridines and phenanthridinones, see:

38b Han W, Zhou X, Yang S, Xiang G, Cui B, Chen Y. J. Org. Chem. 2015; 80: 11580
38c Li L, Chen J.-J, Kan X.-L, Zhang L, Zhao Y.-L, Liu Q. Eur. J. Org. Chem. 2015; 4892

The NHBoc group is, however, tolerated in Negishi couplings of aryl iodides with serine and aspartic acid derived zinc reagents; see:

39a Bender AM, Griggs NW, Gao C, Trask TJ, Traynor JR, Mosberg HI. ACS Med. Chem. Lett. 2015; 6: 1199
39b Usuki T, Yanuma H, Hayashi T, Yamada H, Suzuki N, Masuyama Y. J. Heterocycl. Chem. 2014; 51: 269

40 For a review on heterocyclic boronic acids, see: Tyrrell E, Brookes P. Synthesis 2004; 469
41 Tsou TT, Kochi JK. J. Am. Chem. Soc. 1979; 101: 7547
42 For mechanistic aspects of the named reactions see: Echavarren AM, Homs A. In Metal-Catalyzed Cross-Coupling Reactions and More . Vol 1. de Meijere A, Brase S, Oestreich M. Wiley-VCH; Weinheim: 2014: 1-64
43 See accompanying manuscript: Quesnelle CA, Snieckus V. Synthesis 2018; 50
44 Still WC, Kahn M, Mitra A. J. Org. Chem. 1978; 43: 2923
45 Perrin DD, Armarego WL, Perrin DR. Purification of Laboratory Chemicals 2nd ed. . Pergamon Press; Oxford: 1980
46 Watson SC, Eastham JF. J. Organomet. Chem. 1967; 9: 165
47 Pohmakotr M, Geiss K.-H, Seebach D. Chem. Ber. 1979; 112: 1420
48 Coulson DR. Inorg. Synth. 1972; 13: 121
49 Barnett KW. J. Chem. Educ. 1974; 51: 422
50 Subramanian LR, Hanack M, Chang LW. K, Imhoff MA, Schleyer P. vR, Effenberger F, Kurtz W, Stang PJ, Dueber TE. J. Org. Chem. 1976; 41: 4099
51 Porzelle A, Woodrow MD, Tomkinson NC. O. Org. Lett. 2009; 11: 233
52 Stang P, Anderson AG. J. Org. Chem. 1976; 41: 781
53 Petrakis KS, Nagabhushan TL. J. Am. Chem. Soc. 1987; 109: 2831
54 Nutt RF, Chen K.-M, Jouille MM. J. Org. Chem. 1984; 49: 1013
55 CAQ thanks VS for the preparation of this compound, arguably in the last time he was in the lab.

Supplementary Material

Supporting Information