Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

doi:10.1021/jacs.7b04937

. 2017 Jun 21;139(24):8126-8129.

doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.

Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

Yujing Zhou¹, Jeffrey S Bandar¹, Stephen L Buchwald¹

Affiliations

PMID: 28565905
PMCID: PMC5587210
DOI: 10.1021/jacs.7b04937

Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

Yujing Zhou et al. J Am Chem Soc. 2017.

. 2017 Jun 21;139(24):8126-8129.

doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.

Authors

Yujing Zhou¹, Jeffrey S Bandar¹, Stephen L Buchwald¹

Affiliation

¹ Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.

PMID: 28565905
PMCID: PMC5587210
DOI: 10.1021/jacs.7b04937

Abstract

The direct asymmetric copper hydride (CuH)-catalyzed coupling of α,β-unsaturated carboxylic acids to aryl alkenes to access chiral α-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner.

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Figures

**Scheme 1**
Previous work in hydroacylation using (a) aldehydes, (b) aryl anhydrides, and (c, this work) α,β-unsaturated carboxylic acids to access chiral α-aryl ketones.

**Scheme 2**
(a) Discovery and (b) SAR of CuH-catalyzed tandem hydroacylation and 1,4-reduction with unsaturated acyl electrophiles.^a ^a yields determined by ¹H NMR analysis of crude reaction mixture, (S,S)-Ph-BPE = 1,2-Bis((2S,5S)-2,5-diphenylphospholano)ethane.

**Scheme 3**
Currently proposed pathway for hydroacylation.

**Scheme 4**
The use of (a) acrylic acid and (b) β-ethoxyacrylic acid to access chiral ethyl ketones.^a ^a Yields represent average isolated yields of two runs, performed with 1 mmol of alkene.

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References

1. Corey EJ, Kürti L. Enantioselective Chemical Synthesis: Methods, Logic and Practice. Direct Book Publishing; Dallas: 2010.
1. For general approaches toward quaternary α-aryl ketones, see reference . For reviews on and selected examples of catalytic asymmetric synthesis of quaternary α-aryl ketones: Bellina F, Rossi R. Chem. Rev. 2010;110:1082.Johansson CCC, Colacot TJ. Angew. Chem., Int. Ed. 2010;49:676.Bella M, Gasperi T. Synthesis. 2009;10:1583.Hamada T, Chieffi A, Åhman J, Buchwald SL. J. Am. Chem. Soc. 2002;124:1261.Lia X, Weng Z, Hartwig JF. J. Am. Chem. Soc. 2008;130:195.Trost BM, Schroeder GM, Kristensen J. Angew. Chem., Int. Ed. 2002;41:3492.Kano T, Hayashi Y, Maruoka K. J. Am. Chem. Soc. 2013;135:7134.Xie X, Chen Y, Ma D. J. Am. Chem. Soc. 2006;128:16050.
1. Bordwell FG, Harrelson JA., Jr Can. J. Chem. 1990;68:1714.
1. For reviews and selected examples of asymmetric protonation reactions to access chiral α-aryl ketones, see: Oudeyer S, Briere J-F, Levacher V. Eur. J. Org. Chem. 2014:6103.Mohr JT, Hong AY, Stoltz BM. Nat. Chem. 2009;1:359.Cheon CH, Kanno O, Toste FD. J. Am. Chem. Soc. 2011;133:13248.Cheon CH, Yamamoto H. J. Am. Chem. Soc. 2008;130:9246.Yanagisawa A, Touge T, Arai T. Angew. Chem., Int. Ed. 2005;44:1546.
1. Lundin PM, Esquivias J, Fu GC. Angew. Chem., Int. Ed. 2009;48:154. - PMC - PubMed
2. Lou S, Fu GC. J. Am. Chem. Soc. 2010;132:1264. - PMC - PubMed
3. Cherney AH, Kadunce NT, Reisman SE. J. Am. Chem. Soc. 2013;135:7442. - PubMed
4. Oost R, Misale A, Maulide N. Angew. Chem., Int. Ed. 2016;55:4587. - PubMed
5. Kang BC, Nam DG, Hwang G-S, Ryu DH. Org. Lett. 2015;17:4810. - PubMed

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[1] Corey EJ, Kürti L. Enantioselective Chemical Synthesis: Methods, Logic and Practice. Direct Book Publishing; Dallas: 2010.

[2] Corey EJ, Kürti L. Enantioselective Chemical Synthesis: Methods, Logic and Practice. Direct Book Publishing; Dallas: 2010.

[3] For general approaches toward quaternary α-aryl ketones, see reference . For reviews on and selected examples of catalytic asymmetric synthesis of quaternary α-aryl ketones: Bellina F, Rossi R. Chem. Rev. 2010;110:1082.Johansson CCC, Colacot TJ. Angew. Chem., Int. Ed. 2010;49:676.Bella M, Gasperi T. Synthesis. 2009;10:1583.Hamada T, Chieffi A, Åhman J, Buchwald SL. J. Am. Chem. Soc. 2002;124:1261.Lia X, Weng Z, Hartwig JF. J. Am. Chem. Soc. 2008;130:195.Trost BM, Schroeder GM, Kristensen J. Angew. Chem., Int. Ed. 2002;41:3492.Kano T, Hayashi Y, Maruoka K. J. Am. Chem. Soc. 2013;135:7134.Xie X, Chen Y, Ma D. J. Am. Chem. Soc. 2006;128:16050.

[4] For general approaches toward quaternary α-aryl ketones, see reference . For reviews on and selected examples of catalytic asymmetric synthesis of quaternary α-aryl ketones: Bellina F, Rossi R. Chem. Rev. 2010;110:1082.Johansson CCC, Colacot TJ. Angew. Chem., Int. Ed. 2010;49:676.Bella M, Gasperi T. Synthesis. 2009;10:1583.Hamada T, Chieffi A, Åhman J, Buchwald SL. J. Am. Chem. Soc. 2002;124:1261.Lia X, Weng Z, Hartwig JF. J. Am. Chem. Soc. 2008;130:195.Trost BM, Schroeder GM, Kristensen J. Angew. Chem., Int. Ed. 2002;41:3492.Kano T, Hayashi Y, Maruoka K. J. Am. Chem. Soc. 2013;135:7134.Xie X, Chen Y, Ma D. J. Am. Chem. Soc. 2006;128:16050.

[5] Bordwell FG, Harrelson JA., Jr Can. J. Chem. 1990;68:1714.

[6] Bordwell FG, Harrelson JA., Jr Can. J. Chem. 1990;68:1714.

[7] For reviews and selected examples of asymmetric protonation reactions to access chiral α-aryl ketones, see: Oudeyer S, Briere J-F, Levacher V. Eur. J. Org. Chem. 2014:6103.Mohr JT, Hong AY, Stoltz BM. Nat. Chem. 2009;1:359.Cheon CH, Kanno O, Toste FD. J. Am. Chem. Soc. 2011;133:13248.Cheon CH, Yamamoto H. J. Am. Chem. Soc. 2008;130:9246.Yanagisawa A, Touge T, Arai T. Angew. Chem., Int. Ed. 2005;44:1546.

[8] For reviews and selected examples of asymmetric protonation reactions to access chiral α-aryl ketones, see: Oudeyer S, Briere J-F, Levacher V. Eur. J. Org. Chem. 2014:6103.Mohr JT, Hong AY, Stoltz BM. Nat. Chem. 2009;1:359.Cheon CH, Kanno O, Toste FD. J. Am. Chem. Soc. 2011;133:13248.Cheon CH, Yamamoto H. J. Am. Chem. Soc. 2008;130:9246.Yanagisawa A, Touge T, Arai T. Angew. Chem., Int. Ed. 2005;44:1546.

[9] Lundin PM, Esquivias J, Fu GC. Angew. Chem., Int. Ed. 2009;48:154. - PMC - PubMed

Lou S, Fu GC. J. Am. Chem. Soc. 2010;132:1264. - PMC - PubMed

Cherney AH, Kadunce NT, Reisman SE. J. Am. Chem. Soc. 2013;135:7442. - PubMed

Oost R, Misale A, Maulide N. Angew. Chem., Int. Ed. 2016;55:4587. - PubMed

Kang BC, Nam DG, Hwang G-S, Ryu DH. Org. Lett. 2015;17:4810. - PubMed

[10] Lundin PM, Esquivias J, Fu GC. Angew. Chem., Int. Ed. 2009;48:154. - PMC - PubMed

[11] Lou S, Fu GC. J. Am. Chem. Soc. 2010;132:1264. - PMC - PubMed

[12] Cherney AH, Kadunce NT, Reisman SE. J. Am. Chem. Soc. 2013;135:7442. - PubMed

[13] Oost R, Misale A, Maulide N. Angew. Chem., Int. Ed. 2016;55:4587. - PubMed

[14] Kang BC, Nam DG, Hwang G-S, Ryu DH. Org. Lett. 2015;17:4810. - PubMed

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Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

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Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates

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