Highly Chemoselective and Enantiospecific Suzuki–Miyaura Cross-Couplings of Benzylic Organoboronic Esters

Ben W. Glasspoole; Martins S. Oderinde; Brandon D. Moore; Aurora Antoft-Finch; Cathleen M. Crudden

doi:10.1055/s-0033-1338875

Synthesis, Inhaltsverzeichnis

Synthesis 2013; 45(13): 1759-1763
DOI: 10.1055/s-0033-1338875

paper

Highly Chemoselective and Enantiospecific Suzuki–Miyaura Cross-Couplings of Benzylic Organoboronic Esters

Ben W. Glasspoole

Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada Fax: +1(613)5336669 eMail: cruddenc@chem.queensu.ca

,

Martins S. Oderinde

Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada Fax: +1(613)5336669 eMail: cruddenc@chem.queensu.ca

,

Brandon D. Moore

Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada Fax: +1(613)5336669 eMail: cruddenc@chem.queensu.ca

,

Aurora Antoft-Finch

Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada Fax: +1(613)5336669 eMail: cruddenc@chem.queensu.ca

,

Cathleen M. Crudden*

Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada Fax: +1(613)5336669 eMail: cruddenc@chem.queensu.ca

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Abstract

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This paper is dedicated to Professor Scott E. Denmark, with thanks for his mentorship, his dedication to excellence and his extensive contributions to science.

Abstract

The use of potassium carbonate in addition to silver oxide is shown to increase the enantiospecificity of the Suzuki–Miyaura cross-coupling reaction of chiral secondary benzylic boronic esters. From mechanistic studies, it is shown that the reaction is compatible with Mizoroki–Heck coupling partners, even when they are present in considerable excess. This unique chemoselectivity provides the opportunity to carry out sequential reactions.

Key words

Suzuki - cross-coupling - palladium - chiral - enantiospecific

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Referenzen

References
1 Wilczynski R, Sneddon LG. J. Am. Chem. Soc. 1980; 103: 2857

2a Crudden CM, Edwards D. Eur. J. Org. Chem. 2003; 4695
2b Lata CJ, Crudden CM. J. Am. Chem. Soc. 2010; 132: 131
2c Gonzalez AZ, Roman JG, Gonzalez E, Martinez J, Medina JR, Matos K, Soderquist JA. J. Am. Chem. Soc. 2008; 130: 9218
2d Smith SM, Thacker NC, Takacs JM. J. Am. Chem. Soc. 2008; 130: 3734
2e Vogels CM, Westcott SA. Curr. Org. Chem. 2005; 9: 687
2f Carroll AM, O’Sullivan TP, Guiry PJ. Adv. Synth. Catal. 2005; 347: 609
2g Blume F, Zemolka S, Fey T, Kranich R, Schmalz HG. Adv. Synth. Catal. 2002; 344: 868
2h Vogels CM, Hayes PG, Shaver MP, Westcott SA. Chem. Commun. 2000; 51
2i Ramachandran PV, Jennings MP, Brown HC. Org. Lett. 1999; 1: 1399
2j Beletskaya I, Pelter A. Tetrahedron 1997; 53: 4957
2k Brown JM, Lloyd-Jones GC. J. Am. Chem. Soc. 1994; 116: 866
2l Burgess K, Vanderdonk WA, Westcott SA, Marder TB, Baker RT, Calabrese JC. J. Am. Chem. Soc. 1992; 114: 9350
2m Evans DA, Fu GC, Anderson BA. J. Am. Chem. Soc. 1992; 114: 6679
2n Burgess K, Ohlmeyer MJ. Chem. Rev. 1991; 91: 1179
2o Hayashi T, Matsumoto Y, Ito Y. J. Am. Chem. Soc. 1989; 111: 3426
2p Mannig D, Noth H. Angew. Chem., Int. Ed. Engl. 1985; 24: 878

3a Fernandez E, Maeda K, Hooper MW, Brown JM. Chem. Eur. J. 2000; 6: 1840
3b Fernandez E, Hooper MW, Knight FI, Brown JM. Chem. Commun. 1997; 173

4 Imao D, Glasspoole BW, Laberge VS, Crudden CM. J. Am. Chem. Soc. 2009; 131: 5024

5a Rubina M, Rubin M, Gevorgyan V. J. Am. Chem. Soc. 2003; 125: 7198
5b Luithle JE. A, Pietruszka J. J. Org. Chem. 1999; 64: 8287
5c Wang X.-Z, Deng M.-Z. J. Chem. Soc., Perkin Trans. 1 1996; 2663

6a Dreher SD, Dormer PG, Sandrock DL, Molander GA. J. Am. Chem. Soc. 2008; 130: 9257
6b van den Hoogenband A, Lange JH. M, Terpstra JW, Koch M, Visser GM, Visser M, Korstanje TJ, Jastrzebski JT. B. H. Tetrahedron Lett. 2008; 49: 4122

7 Molander GA, Wisniewski SR. J. Am. Chem. Soc. 2012; 134: 16856

8a Awano T, Ohmura T, Suginome M. J. Am. Chem. Soc. 2011; 133: 20738
8b Ohmura T, Awano T, Suginome M. J. Am. Chem. Soc. 2010; 132: 13191

9 Lee JC. H, MacDonald R, Hall DG. Nat. Chem. 2011; 3: 894
10 Glasspoole BW, Ghozati K, Moir J, Crudden CM. Chem. Commun. 2012; 48: 1230
11 Partridge BM, Chausset-Boissarie L, Burns M, Pulis AP, Aggarwal VK. Angew. Chem. Int. Ed. 2012; 51: 11795
12 Molander GA, Ito T. Org. Lett. 2001; 3: 393
13 Glasspoole BW. PhD Dissertation. Queen’s University; Canada: 2011

For an example of a system where a Mizoroki–Heck reaction occurs to the exclusion of Suzuki–Miyaura coupling, see:

14a Itami K, Tonogaki K, Ohashi Y, Yoshida J.-I. Org. Lett. 2004; 6: 4093
14b Itami K, Tonogaki K, Nokami T, Ohashi Y, Yoshida J.-I. Angew. Chem. Int. Ed. 2006; 45: 2404

15 Note that Falck reported the use of both silver oxide and potassium carbonate in the coupling of linear alkyl boronic acids, see: Zou G, Krishna Reddy Y, Falck JR. Tetrahedron Lett. 2001; 42: 7213
16 Note that this is not the case for the coupling of allylic boronic esters where only a 2:1 phosphine/Pd ratio is sufficient, see: Chausset-Boissarie, L.; Ghozati, K.; LaBine, E.; Chen, J. L.-Y.; Aggarwal, V. K.; Crudden, C. M. manuscript submitted for publication.
17 The addition of trace amounts of water has been found to increase the yield at the expense of enantiospecificity, even in the presence of potassium carbonate. The use of approximately 300 ppm of degassed water is typically employed in cases where yield is an issue.¹³ If the yield of the reaction is good, water can be omitted.¹⁶ These results will be described in more detail in a future publication.
18 Note that in couplings of 1-iodonaphthalene (1h), the presence of trace amounts of naphthalene were observed, consistent with the possible intermediacy of III, from which reductive elimination produces naphthalene.
19 Hills ID, Netherton MR, Fu GC. Angew. Chem. Int. Ed. 2003; 42: 5749
20 Armarego WL. F, Perrin DD. Purification of Laboratory Chemicals . 4th ed. Pergamon; New York: 1997