Abstract
An asymmetric monoborylation of alkenylsilanes catalyzed by a copper(I) complex with chiral bisphosphine ligand BenzP* is reported. The reaction proceeded with excellent regioselectivity and high enantioselectivity to afford the corresponding optically active organoboronate esters with a stereogenic C–B bond containing a vicinal silyl group. The synthetic utility of the product is demonstrated through stepwise transformations to multifunctional optically active compounds in a stereospecific manner.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Hall DG (ed) (2011) Boronic acids: preparation and applications in organic synthesis, medicine and materials, 2nd revised edn. Wiley-VCH, Weinheim
Stymiest JL, Bagutski V, French RM, Aggarwal VK (2008) Nature 456:778
Ito H, Ito H, Yamanaka H, Yamanaka H, Tateiwa J, Tateiwa J, Hosomi A, Hosomi A (2000) Tetrahedron Lett 41:6821
Takahashi K, Ishiyama T, Miyaura N (2000) Chem Lett:982
Ito H, Kawakami C, Sawamura M (2005) J Am Chem Soc 127:16034
Ito H, Ito S, Ito S, Sasaki Y, Sasaki Y, Matsuura K, Matsuura K, Sawamura M, Sawamura M (2007) J Am Chem Soc 129:14856
Ito H, Kosaka Y, Nonoyama K, Sasaki Y, Sawamura M (2008) Angew Chemie Int Ed 47:7424
Ito H, Ito H, Sasaki Y, Sasaki Y, Sawamura M, Sawamura M (2008) J Am Chem Soc 130:15774
Sasaki Y, Zhong C, Sawamura M, Ito H (2010) J Am Chem Soc 132:1226
Zhong C, Kunii S, Kosaka Y, Sawamura M, Ito H (2010) J Am Chem Soc 132:11440
Ito H, Okura T, Matsuura K, Sawamura M (2010) Angew Chem Int Ed 49:560
Ito H, Toyoda, Sawamura M (2010) J Am Chem Soc 132:5990
Ito H, Kunii S, Sawamura M (2010) Nat Chem 2:972
Sasaki Y, Sasaki Y, Horita Y, Horita Y, Zhong C, Zhong C, Sawamura M, Sawamura M, Ito H, Ito H (2011) Angew Chemie Int Ed 50:2778
Lee J-E, Lee J-E, Yun J, Yun J (2008) Angew Chemie Int Ed 47:145
Lillo V, Prieto A, Bonet A, Diaz-Requejo MM, Ramirez J, Perez PJ, Fernandez E (2009) Organometallics 28:659
Lee Y, Hoveyda AH (2009) J Am Chem Soc 131:3160
Noh D, Chea H, Ju J, Yun J (2009) Angew Chemie Int Ed 48:6062
Chen I-H, Yin L, Itano W, Kanai M, Shibasaki M (2009) J Am Chem Soc 131:11664
O’Brien JM, Lee K-S, Hoveyda AH (2010) J Am Chem Soc 132:10630
Moure AL, Gómez Arrayás R, Carretero JC (2011) Chem Commun 47:6701
Solé C, Solé C, Whiting A, Whiting A, Gulyás H, Gulyás H, Fernandez E, Fernandez E (2011) Adv Synth Catal 353:376
Corberán R, Mszar NW, Hoveyda AH (2011) Angew Chemie Int Ed 50:7079
Lee JCH, McDonald R, Hall DG (2011) Nat Chem 3:894
Feng X, Feng X, Jeon H, Jeon H, Yun J, Yun J (2013) Angew Chemie Int Ed 52:3989
Hayashi T, Matsumoto Y, Ito Y (1989) J Am Chem Soc 111:3426
Rubina M, Rubin M, Gevorgyan V (2003) J Am Chem Soc 125:7198
Crudden CM, Hleba YB, Chen AC (2004) J Am Chem Soc 126:9200
Lee Y, Hoveyda AH (2009) J Am Chem Soc 131:3160; (e) Noh D, Chea H, Ju J, Yun J (2009) Angew Chem Int Ed 48:6062
Smith SM, Thacker NC, Takacs JM (2008) J Am Chem Soc 130:3734
Burns AR, Solana González J, Lam HW (2012) Angew Chemie Int Ed 51:10827
Matsuda N, Hirano K, Satoh T, Miura M (2013) J Am Chem Soc 135:4934
Miura K, Hondo T, Nakagawa T, Takahashi T, Hosomi A (2000) Organ Lett 2:385
Murakami M, Suginome M, Fujimoto K, Nakamura H, Andersson PG, Ito Y (1993) J Am Chem Soc 115:6487
Brinkmann AE, Berger S, Brauman I (1994) J Am Chem Soc 116:8304
Mun S, Lee J-E, Yun J (2006) Organ Lett 8:4887
Meng F, Jang H, Hoveyda AH (2013) Chem Euro J 19:3204
Imamoto T, Sugita K, Yoshida K (2005) J Am Chem Soc 127:11934–11935
Imamoto T, Tamura K, Zhang Z, Horiuchi Y, Sugiya M, Yoshida K, Yanagisawa A, Gridnev ID (2012) J Am Chem Soc 134:1754
Dang L, Zhao H, Lin Z, Marder TB (2008) Organometallics 27:1178
Dang L, Lin ZY, Marder TB (2009) Chem Commun:3987
Ligand effect on the addition of borylcopper(I) complex to unactivated terminal alkenes has been discussed based on DFT caluculations (B3PW91/cc-pVDZ), see: Kubota K, Yamamoto E, Ito H (2013) J Am Chem Soc 135:2625
Ito H, Kubota K (2012) Organ Lett 14:890
Yang C-T, Zhang Z-Q, Tajuddin H, Wu C-C, Liang J, Liu J-H, Fu Y, Czyzewska M, Steel PG, Marder TB, Liu L (2011) Angew Chemie Int Ed 51:528
Kleeberg C, Dang L, Lin Z, Marder TB (2009) Angew Chemie Int Ed 48:5350
Kabalka GW, Shoup TM, Goudgaon NM (1989) J Organ Chem 54:5930
Hupe E, Marek I, Knochel P (2002) Organ Lett 4:2861
The reaction of (Z)-1a with 2 in the presence of 5 mol % of CuCl/PPh3 catalyst gave 16% of (rac)-3a unedr the same conditions for Table 1. Use of IMes resulted in 80% yield of (rac)-3a
Gaussian 09, Revision C.01, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ, Gaussian Inc., Wallingford CT (2009)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2017 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Kubota, K. (2017). Copper(I)-Catalyzed Regio- and Enantioselective Monoborylation of Alkenylsilanes. In: Synthesis of Functionalized Organoboron Compounds Through Copper(I) Catalysis. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-4935-4_4
Download citation
DOI: https://doi.org/10.1007/978-981-10-4935-4_4
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-4934-7
Online ISBN: 978-981-10-4935-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)