Efficient Synthesis of β-Oxoalkyl Carbamates from Carbon Dioxide, Internal Propargylic Alcohols, and Secondary Amines Catalyzed by Silver Salts and DBU

Abstract

The three-component reaction of internal propargylic alcohols with secondary amines and carbon dioxide proceeded smoothly in the presence of a catalyst system comprising a silver salt and 1,8-diazabicyclo[5.4.0]undec-7-ene in 1,4-dioxane at 90 ˚C to give the corresponding β-oxoalkyl carbamates in good to high yields. The counterion of the silver salt had little effect on the reaction whereas the nature of the organic base had a marked influence.

amines - carbamates - carbon dioxide - catalysis - propargylic alcohols

References

<A NAME="RF23909SS-1A">1a</A> Sakakura H. Choi J.-C. Yasuda H. Chem. Rev.  2007,  107:  2365 

<A NAME="RF23909SS-1B">1b</A> Darensbourg DJ. Chem. Rev.  2007,  107:  2388 

<A NAME="RF23909SS-1C">1c</A> Beckman EJ. Ind. Eng. Chem. Res.  2003,  42:  1598 

<A NAME="RF23909SS-1D">1d</A> Shi M. Shen Y.-M. Curr. Org. Chem.  2003,  7:  737 

<A NAME="RF23909SS-2A">2a</A> Salvatore RN. Flanders VL. Ha D. Jung KW. Org. Lett.  2000,  2:  2797 

<A NAME="RF23909SS-2B">2b</A> Yoshida D. Hara N. Okuyama S. Chem. Commun.  2000,  151 

<A NAME="RF23909SS-2C">2c</A> Rohr M. Geyer C. Wandeler R. Schneider MS. Murphy EF. Baiker A. Green Chem.  2001,  3:  123 

<A NAME="RF23909SS-2D">2d</A> Salvatore SI. Shin SI. Nagle AS. Jung KWJ. Org. Chem.  2001,  66:  1035 

<A NAME="RF23909SS-2E">2e</A> Abla M. Choi J.-C. Sakakura T. Chem. Commun.  2001,  2238 

<A NAME="RF23909SS-2F">2f</A> Feroci M. Casadei MA. Orsini M. Palombi L. Inesi A. J. Org. Chem.  2003,  68:  1548 

<A NAME="RF23909SS-2G">2g</A> Srivastava R. Srinivas D. Ratnasamy P. Appl. Catal. A  2005,  289:  128 

<A NAME="RF23909SS-2H">2h</A> Chaturvedi D. Ray S. Monatsh. Chem.  2006,  137:  127 

<A NAME="RF23909SS-2I">2i</A> Chaturvedi D. Mishra N. Mishra V. Monatsh. Chem.  2007,  138:  57 

<A NAME="RF23909SS-3A">3a</A> Vauthey I. Valot F. Gozzi C. Fache F. Lemaire M. Tetrahedron Lett.  2000,  41:  6347 

<A NAME="RF23909SS-3B">3b</A> Wu TT. Huang J. Arrington ND. Dill GM. J. Agric. Food Chem.  1987,  35:  817 

<A NAME="RF23909SS-3C">3c</A> Barthelemy L. Lyon Pharm.  1986,  37:  249 

<A NAME="RF23909SS-3D">3d</A> Adams P. Baron FA. Chem. Rev.  1965,  65:  567 

<A NAME="RF23909SS-4">4</A> Green TW. Wuts PGM. Protective Groups in Organic Synthesis   2nd ed.:  Wiley; New York: 1999.  p.315-318  

<A NAME="RF23909SS-5A">5a</A> Sasaki Y. Dixneuf PH. J. Org. Chem.  1987,  52:  4389 

<A NAME="RF23909SS-5B">5b</A> Burncau C. Dixneuf PH. Tetrahedron Lett.  1987,  28:  2005 

<A NAME="RF23909SS-5C">5c</A> Sasaki Y. inventors; JP  62061961(A).  ; Chem. Abstr. 1988, 108, 204234

<A NAME="RF23909SS-6">6</A> Kim TJ. Kwon KH. Kwon SC. Baeg JO. Shim SC. Lee DH. J. Organomet. Chem.  1990,  389:  205 

<A NAME="RF23909SS-7">7</A> Shim SC. Baeg JO. Doh CH. Young YZ. Kim TJ. Bull. Korean Chem. Soc.  1990,  11:  467 

<A NAME="RF23909SS-8A">8a</A> Kim H.-S. Kim J.-W. Kwon S.-C. Shim S.-C. Kim T.-J. J. Organomet. Chem.  1997,  545-546:  337 

<A NAME="RF23909SS-8B">8b</A> Kwon S.-C. Cho S.-C. Shim S.-C. Kim T.-J. Bull. Korean Chem. Soc.  1999,  20:  103 

<A NAME="RF23909SS-9A">9a</A> Qi CR. Jiang HF. Wang ZY. Zou B. Yang SR. Synlett  2007,  255 

<A NAME="RF23909SS-9B">9b</A> Qi CR. Jiang HF. Wang ZY. Zou B. Chin. J. Chem.  2007,  25:  1051 

<A NAME="RF23909SS-9C">9c</A> Qi CR. Jiang HF. Liu HL. Yang SR. Zou B. Gaodeng Xuexiao Huaxue Xuebao  2007,  28:  1084 ; Chem. Abstr. 2007, 148, 538111

<A NAME="RF23909SS-9D">9d</A> Jiang HF. Wang AZ. Liu HL. Qi CR. Eur. J. Org. Chem.  2008,  2309 

<A NAME="RF23909SS-9E">9e</A> Jiang H. Zhao J. Wang A. Synthesis  2008,  763 

<A NAME="RF23909SS-9F">9f</A> Jiang HF. Zhao JW. Tetrahedron Lett.  2009,  50:  60 

<A NAME="RF23909SS-10">10</A> Qi CR. Jiang HF. Green Chem.  2007,  9:  1284 

<A NAME="RF23909SS-11">11</A>

(4Z)-4-Benzylidene-1,3-dioxaspiro[4.5]decan-2-one could be quantitatively transformed into 3a by treatment with Et₂NH (1 equiv) in 1,4-dioxane at 90 ˚C for 15 h.

<A NAME="RF23909SS-12">12</A>

When a primary amine(butylamine) was used under the same conditions, 4-benzylidene-3-butyl-1-oxa-3-azaspiro[4.4]nonan-2-one was obtained in 81% yield (E/Z = 52:48).

<A NAME="RF23909SS-13A">13a</A> Bruneau C. Dixneuf PH. J. Mol. Catal.  1992,  74:  97 

<A NAME="RF23909SS-13B">13b</A> Inoue Y. Ishikawa J. Taniguchi M. Hashimoto H. Bull. Chem. Soc. Jpn.  1987,  60:  1204 

<A NAME="RF23909SS-13C">13c</A> Fujiwara S. Shikano Y. Shinike T. Kambe N. Sonoda N. J. Org. Chem.  2002,  67:  6275 

<A NAME="RF23909SS-13D">13d</A> Kayaki Y. Yamamoto M. Suzuki T. Ikariya T. Green Chem.  2006,  8:  1019 

<A NAME="RF23909SS-13E">13e</A> Yamada W. Sugawara Y. Cheng HM. Ikeno T. Yamada T. Eur. J. Org. Chem.  2007,  2604