Highly Efficient and Facile Aryl Transfer to Aldehydes Using ArB(OH)₂-GaMe₃

Abstract

A rapid and efficient procedure for the synthesis of di­arylmethanols has successfully been achieved by the aryl transfer to aldehydes using the ArB(OH)₂-GaMe₃ combined systems in excellent yields (up to 98%) at room temperature.

Key words

aryl transfer - benzaldehyde - phenylboronic acid - tri­methylgallium - diarylmethanol

References and Notes

• 1a Harms AF. Nauta WT. J. Med. Pharm. Chem.  1960,  2:  57 
• 1b Bolshan Y. Chen C.-Y. Chilenski JR. Gosselin F. Mathre DJ. O’Shea PD. Roy A. Tillyer RD. Org. Lett.  2004,  6:  111 
• 1c Seto M. Aramaki Y. Imoto H. Akiwa K. Oda T. Kanzaki N. Iizawa Y. Baba M. Shiraishi M. Chem. Pharm. Bull.  2004,  52:  818 
• For related reviews, see:
• 1d Bolm C. Hildebrand JP. Muiz K. Hermanns N. Angew. Chem. Int. Ed.  2001,  40:  3284 
• 1e Schmidt F. Stemmler RT. Rudolph J. Bolm C. Chem. Soc. Rev.  2006,  35:  454 
• 2a Sakai M. Ueda M. Miyaura N. Angew. Chem. Int. Ed.  1998,  37:  3279 
• 2b Ueda M. Miyaura N. J. Org. Chem.  2000,  65:  4450 
• 3a Fürstner A. Krause H. Adv. Synth. Catal.  2001,  343:  343 
• 3b Son SU. Kim SB. Reingold JA. Carpenter GB. Sweigart DA. J. Am. Chem. Soc.  2005,  127:  12238 
• 3c Chen JH. Zhang XQ. Feng Q. Luo MM.
  J. Organomet. Chem.  2006,  691:  470 
• 3d Gois PMP. Trindade AF. Veiros LF. André V. Duarte MT. Afonso CAM. Caddick S. Cloke FGN. Angew. Chem. Int. Ed.  2007,  46:  5750 
• 4a Yamamoto T. Ohta T. Ito Y. Org. Lett.  2005,  7:  4153 
• 4b Suzuki K. Arao T. Ishii S. Maeda Y. Kondo K. Aoyama T. Tetrahedron Lett.  2006,  47:  5789 
• 4c Qin CM. Wu HY. Cheng J. Chen XA. Liu MC. Zhang WW. Su WK. Ding JC. J. Org. Chem.  2007,  72:  4102 
• 4d He P. Lu Y. Hu Q.-S. Tetrahedron Lett.  2007,  48:  5283 
• 4e He P. Lu Y. Dong C.-G. Hu Q.-S. Org. Lett.  2007,  9:  343 
• 4f Lin SH. Lu XY. J. Org. Chem.  2007,  72:  9757 
• 5a Takahashi G. Shirakawa E. Tsuchimoto T. Kawakami Y. Chem. Commun.  2005,  1459 
• 5b Arao T. Kondo K. Aoyama T. Tetrahedron Lett.  2007,  48:  4115 
• 6a Bolm C. Hermanns N. Hildebrand JP. Nuniz K. Angew. Chem. Int. Ed.  2000,  39:  3465 
• 6b Bolm C. Kesselgruber M. Hermanns N. Hildebrand JP. Angew. Chem. Int. Ed.  2001,  39:  1488 
• 7a Bolm C. Rudolph J. J. Am. Chem. Soc.  2002,  124:  14850 
• 7b Rudolph J. Hermanns N. Bolm C. J. Org. Chem.  2004,  69:  3997 
• 8a Ji J.-X. Wu J. Au-Yeung TT.-L. Yip C.-W. Haynes RK. Chan ASC. J. Org. Chem.  2005,  70:  1093 
• 8b Braga AL. Lüdtke DS. Schneider PH. Vargas F. Schneider A. Wessjohann LA. Paixão MW. Tetrahedron Lett.  2005,  46:  7827 
• 8c Braga AL. Lüdtke DS. Vargas F. Paixão MW. Chem. Commun.  2005,  2512 
• 8d Braga AL. Milani P. Vargas F. Paixão MW. Sehnem JA. Tetrahedron: Asymmetry  2006,  17:  2793 
• 8e Paixão MW. Godoi M. Rhoden CRB. Westermann B. Wessjohann L. Lüdtke DS. Braga AL. J. Mol. Catal. A: Chem.  2007,  261:  120 
• 8f Jin M.-J. Sarkar SM. Lee D.-H. Qiu HL. Org. Lett.  2008,  10:  1235 
• 8g Jimeno C. Sayalero S. Fjermestad T. Colet G. Maseras F. Pericàs MA. Angew. Chem. Int. Ed.  2008,  47:  1098 
• 8h Fontes M. Verdaguer X. Solà L. Pericàs MA. Riera A. J. Org. Chem.  2004,  69:  2532 
• 9a Nishimura Y. Miyake Y. Amemiya R. Yamaguchi M. Org. Lett.  2006,  8:  5077 
• 9b Nishimura Y. Amemiya R. Yamaguchi M. Tetrahedron Lett.  2006,  47:  1839 
• 9c Nishimura Y. Shiraishi T. Yamaguchi M. Tetrahedron Lett.  2008,  49:  3492 
• 10a Zhu CJ. Yuan F. Gu WJ. Pan Y. Chem. Commun.  2003,  692 
• 10b Yuan F. Zhu CJ. Sun JT. Liu YJ. Pan Y. J. Organomet. Chem.  2003,  682:  102 
• 11 Dai ZY. Zhu CJ. Yang MH. Zheng YF. Pan Y. Tetrahedron: Asymmetry  2005,  16:  605 
• 12 Jia XF. Yang HW. Fang L. Zhu CJ. Tetrahedron Lett.  2008,  49:  1370 

13

General Experimental Procedure
The arylboronic acid (0.3 mmol, 1.5 equiv) was dissolved in anhyd toluene (2 mL) in a 20 mL flame-dried Schlenk reaction tube under argon atmosphere. A commercially available 1 M solution of Me₃Ga in toluene (0.9 mmol, 4.5 equiv) was added via syringe dropwise, and the resulting mixture was stirred for 2 h at r.t. followed by the addition of aldehyde (0.2 mmol). After completion of the reaction (monitored by TLC), the reaction solution was quenched with H₂O (3 mL) and further extracted with EtOAc (3 × 5 mL). The combined organic layer was dried over Na₂SO₄. Evaporation of the solvent gave the crude product, which was further purified by preparative TLC (PE-EtOAc, 5:1) to give corresponding pure diarylmethanols.

14

The reactivity of nitro-substituted benzaldehyde is in agreement with the experimental results in references 3c, 4d-f, but 4-nitrobenzaldehyde is not reactive in reference 2a.

15

In reference 8g,h, the mechanism of the boron-to-zinc transmetalation has been clarified by theoretical calculations and experimental study. In this process, the mixed zinc species (ArZnEt) is formed.