Weinreb Amide Based Building Blocks for the Synthesis of α- and β-Organylseleno Aryl Ketones

Abstract

A new strategy for the synthesis of α- and β-organylseleno aryl ketones has been achieved. The strategy is based on the use of hitherto unreported 2,2′-diselenediylbis(N-methoxy-N-methyl­acetamide) and 3,3′-diselenediylbis(N-methoxy-N-methylpropan­amide). The envisaged synthetic equivalents combine the usefulness of Weinreb amide (WA) functionality and those innate with selenium for the first time. The synthesis of the targets, α- and β-organylseleno aryl ketones could be achieved by the reductive cleavage of Se-Se bond, followed by the alkylation on selenium, and the addition of arylmagnesium halide onto the WA functionality therein.

Weinreb amide - reductive alkylation - glycosylseleno ketones - Grignard addition

References and Notes

<A NAME="RB06611ST-1">1</A> Freudendahl DM. Shahzad SA. Wirth T. Eur. Org. Chem.  2009,  1649 

<A NAME="RB06611ST-2A">2a</A> Braga HC. Stefani HA. Paixao MW. Santos FW. Ludtke DS. Tetrahedron  2010,  66:  3441 

<A NAME="RB06611ST-2B">2b</A> Braga HC. Wouters AD. Zerillo FB. Ludtke DS. Carbohydr. Res.  2010,  345:  2328 

<A NAME="RB06611ST-3A">3a</A> Victoria FN. Radatz CS. Sachini M. Jacob RG. Perin G. Da Silva WP. Lenardão EJ. Tetrahedron Lett.  2009,  50:  6761 ; and references cited therein

<A NAME="RB06611ST-3B">3b</A> Paulmier C. Houllemare D. Ponthieux S. Outurquin F. Synthesis  1997,  101 

<A NAME="RB06611ST-3C">3c</A> Cossy J. Furet N. Tetrahedron Lett.  1993,  34:  7755 

<A NAME="RB06611ST-3D">3d</A> Magnus P. Rigollier P. Tetrahedron Lett.  1992,  33:  6111 

<A NAME="RB06611ST-3E">3e</A> Back T. Kerr R. Tetrahedron Lett.  1982,  23:  3241 

<A NAME="RB06611ST-3F">3f</A> Sonoda N. Miyoshi N. Yamamoto T. Kambe N. Murai S. Tetrahedron Lett.  1982,  23:  4813 

<A NAME="RB06611ST-4">4</A> Bao W. Zhang Y. Synlett  1996,  1187 

<A NAME="RB06611ST-5">5</A> Nishiyama Y. Kawamatsu H. Funato S. Tokunaga K. Sonoda N. J. Org. Chem.  2003,  68:  3599 

<A NAME="RB06611ST-6">6</A> Reich HJ. Jasperse CP. Renga JM. J. Org. Chem.  1986,  51:  2981 

<A NAME="RB06611ST-7A">7a</A> Meciarova M. Toma S. Lett. Org. Chem.  2006,  3:  794 

<A NAME="RB06611ST-7B">7b</A> Chu C.-M. Gao S. Sastry MNV. Kuo C.-W. Lu C. Liu J.-T. Yao C.-F. Tetrahedron  2007,  63:  1863 ; and references cited therein

<A NAME="RB06611ST-8A">8a</A> Nahm S. Weinreb SM. Tetrahedron Lett.  1981,  22:  3815 

For reviews on Weinreb amide chemistry, see:

<A NAME="RB06611ST-8B">8b</A> Sivaraman B. Aidhen IS. Synthesis  2008,  3707 

<A NAME="RB06611ST-8C">8c</A> Singh J. Satyamurthi N. Aidhen IS. J. Prakt. Chem.  2000,  342:  340 

<A NAME="RB06611ST-8D">8d</A> Mentzel M. Hoffmann HMR.
J. Prakt. Chem.  1997,  339:  517 

<A NAME="RB06611ST-8E">8e</A> Sibi MP. Org. Prep. Proced. Int.  1993,  25:  15 

<A NAME="RB06611ST-9A">9a</A> Sivaraman B. Harikrishna K. Aidhen IS. Tetrahedron Lett.  2011,  52:  2683 

<A NAME="RB06611ST-9B">9b</A> Sivaraman B. Aidhen IS. Eur. J. Org. Chem.  2010,  4991 

<A NAME="RB06611ST-9C">9c</A> Sivaraman B. Senthilmurugan A. Aidhen IS. Synlett  2007,  2841 

<A NAME="RB06611ST-9D">9d</A> Sivaraman B. Aidhen IS. Synlett  2007,  959 

<A NAME="RB06611ST-10">10</A> Logan G. Igunbor C. Chen G.-X. Davis H. Simon A. Salon J. Synlett  2006,  1554 

<A NAME="RB06611ST-11">11</A> Klayman DL. Griffin TS. J. Am. Chem. Soc.  1973,  95:  197 

<A NAME="RB06611ST-12">12</A> Ghosh AK. Banerjee S. Sinha S. Kang SB. Zajc B. J. Org. Chem.  2009,  74:  3689 

<A NAME="RB06611ST-13">13</A> Selvamurugan V. Aidhen IS. Synthesis  2001,  2239 

<A NAME="RB06611ST-14">14</A>

2,2′-Diselenediylbis( N -methoxy- N -methylacetamide) (4) Yield 45%. R _f = 0.20 (hexanes-EtOAc = 6:4), yellow colored liquid. ^¹H NMR (400 MHz, CDCl₃): δ = 3.14 (s, 3 H, NCH₃), 3.52 (s, 2 H, SeCH₂), 3.68 (s, 3 H, OCH₃). ^¹³C NMR (100 MHz, CDCl₃): δ = 29.6, 32.5, 61.5, 171.2. IR (CHCl₃): 2929, 2850, 1637, 1445, 1155 cm^-¹. ESI-HRMS: m/z calcd for C₈H₁₆N₂O₄NaSe₂ [M + Na]⁺: 386.9338; found: 386.9344.
3,3′-Diselenediylbis( N -methoxy- N -methylpropan-amide) (5)
Yield 65%. R _f =0.25 (hexanes-EtOAc = 6:4), yellow colored liquid. ^¹H NMR (400 MHz, CDCl₃): δ = 2.94-2.98 (m, 2 H, COCH₂), 3.12-3.15 (m, 2 H, SeCH₂), 3.19 (s, 3 H, NCH₃), 3.70 (s, 3 H, OCH₃). ^¹³C NMR (100 MHz, CDCl₃): δ = 22.1, 29.1, 32.4, 61.5, 171.5. IR (CHCl₃): 2921, 2847, 1626, 1458, 1166 cm^-¹. ESI-HRMS: m/z calcd for C₁₀H₂₁N₂O₄Se₂ [M + H]⁺: 392.9832; found: 392.9833.

<A NAME="RB06611ST-15">15</A>

The sugar halides 13 and 14 were prepared through multistep reaction sequence from commercially available monosacchride d-(+)-glucono-1,5-lactone.

<A NAME="RB06611ST-16">16</A> Déziel R. Malenfant E. Thibault C. Fréchette S. Gravel M. Tetrahedron Lett.  1997,  38:  4753 

<A NAME="RB06611ST-17">17</A> Campbell TW. McCullough JD. J. Am. Chem. Soc.  1945,  67:  1965