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DOI: 10.1055/s-0031-1289854
Catalytic Enantioselective Arylation of Aldehydes by Using Functionalized Grignard Reagents Generated from Aryl Bromides
Publication History
Publication Date:
09 November 2011 (online)
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Abstract
An efficient catalytic method has been developed for the enantioselective synthesis of functionalized diarylmethanols starting from aryl bromides and aldehydes. In the presence of (R)-3-(3,5-diphenylphenyl)BINOL (2 mol%) and titanium tetraisopropoxide, functionalized aryl Grignard reagents (FGArMgCl; FG = 3-F3C, 4-F3C, 3-Br, 3-CN, 4-CN), prepared in situ by treatment of the bromides with i-PrMgCl˙LiCl, undergo addition to aldehydes to give the corresponding functionalized diarylmethanols in high enantioselectivities.
Key words
aldehydes - arylation - asymmetric catalysis - magnesium - titanium
- Supporting Information for this article is available online:
- Supporting Information
- Review:
-
1a
Schmidt F.Stemmler RT.Rudolph J.Bolm C. Chem. Soc. Rev. 2006, 35: 454 -
1b
Paixão MW.Braga AL.Lüdtke DS. J. Braz. Chem. Soc. 2008, 19: 813 -
2a
Sakai M.Ueda M.Miyaura N. Angew. Chem. Int. Ed. 1998, 37: 3279 -
2b
Yamamoto Y.Kurihara K.Miyaura N. Angew. Chem. Int. Ed. 2009, 48: 4414 -
2c
Nishimura T.Kumamoto H.Nagaosa M.Hayashi T. Chem. Commun. 2009, 5713 -
2d
Morikawa S.Michigami K.Amii H. Org. Lett. 2010, 12: 2520 -
2e
Karthikeyan J.Jeganmohan M.Cheng C.-H. Chem. Eur. J. 2010, 16: 8989 ; and references cited therein -
3a
Bolm C.Rudolph J. J. Am. Chem. Soc. 2002, 124: 14850 -
3b
Schmidt F.Rudolph J.Bolm C. Adv. Synth. Catal. 2007, 349: 703 -
3c
Wang X.-B.Kodama K.Hirose T.Yang X.-F.Zhang G.-Y. Tetrahedron: Asymmetry 2010, 21: 75 -
3d
Wouters AD.Trossini GHG.Stefani HA.Lüdtke DS. Eur. J. Org. Chem. 2010, 2351 -
3e
Moro AV.Tiekink ERT.Zukerman-Schpector J.Lüdtke DS.Correia CRD. Eur. J. Org. Chem. 2010, 3696 ; and references cited therein -
4a
Shannon J.Bernier D.Rawson D.Woodward S. Chem. Commun. 2007, 3945 -
4b
Glynn D.Shannon J.Woodward S. Chem. Eur. J. 2010, 16: 1053 -
5a
Muramatsu Y.Harada T. Angew. Chem. Int. Ed. 2008, 47: 1088 -
5b
Muramatsu Y.Harada T. Chem. Eur. J. 2008, 14: 10560 -
5c
Muramatsu Y.Kanehira S.Tanigawa M.Miyawaki Y.Harada T. Bull. Chem. Soc. Jpn. 2010, 83: 19 -
5d
Nakagawa Y.Muramatsu Y.Harada T. Eur. J. Org. Chem. 2010, 6535 - Review:
-
6a
Knochel P.Dohle W.Gommermann N.Kneisel FF.Kopp F.Korn T.Sapountzis I.Vu VA. Angew. Chem. Int. Ed. 2003, 42: 4302 -
6b
Knochel P.Krasovskiy A.Sapountzis I. In Handbook of Functionalized Organometallics Vol. 1:Knochel P. Wiley-VCH; Weinheim: 2005. p.109 -
6c
Hiriyakkanavar I.Baron O.Wagner AJ.Knochel P. Chem. Commun. 2006, 583 -
7a
Boymond L.Rottlander M.Cahiez G.Knochel P. Angew. Chem. Int. Ed. 1998, 37: 1701 -
7b
Krasovskiy A.Knochel P. Angew. Chem. Int. Ed. 2004, 43: 3333 -
7c
Shi L.Chu Y.Knochel P.Mayr H. J. Org. Chem. 2009, 74: 2760 -
7d
Piller FM.Metzger A.Schade M.Haag BA.Gavryushin A.Knochel P. Chem. Eur. J. 2009, 15: 7192 - 8
Fillon H.Gosmini C.Périchon J. J. Am. Chem. Soc. 2003, 125: 3867 - 9
Leazer JL.Cvetovich R.Tsay F.-R.Dolling U.Vickery T.Bachert D. J. Org. Chem. 2003, 68: 3695 - 10
Welch JT.Eswarakrishnan S. Fluorine in Bioorganic Chemistry John Wiley and Sons; New York: 1991. p.246
References and Notes
The mixed titanium reagent of 2-MeOC6H4MgBr and Ti(Oi-Pr)4 also underwent nonenantioselective reaction to an aldehyde.5c Intramolecular coordination of the ortho substituents to the titanium center might be responsible for the poor selectivities.