A Cyclocarbonylation for the Synthesis of Bicyclic 3-Methylene-1-phthal­imidoylbutyrolactams from Allene-hydrazones Mediated by Mo(CO)₆

Abstract

A novel carbonylative cyclization for the synthesis of cis-fused bicyclic 3-methylenebutyrolactams from allene-hydrazone functionalities mediated by Mo(CO)₆ with DMSO is described. Dramatic solvent effect of CH₂Cl₂ was observed to expedite the process to afford the cyclized products in good yields.

allenes - carbonylation - cyclizations - hydrazones - ­molybdenum

References and Notes

<A NAME="RU04207ST-1A">1a</A> For general discussions, see: Transition Metals for Organic Synthesis   Vol. I:  Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. 

<A NAME="RU04207ST-1B">1b</A> Transition Metals for Organic Synthesis   Vol. II:  Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. 

<A NAME="RU04207ST-2A">2a</A> Ojima I. Tzamarioudaki M. Li Z. Donovan R. Chem. Rev.  1996,  96:  635 

<A NAME="RU04207ST-2B">2b</A> Lautens M. Klute W. Tam W. Chem. Rev.  1996,  96:  49 

<A NAME="RU04207ST-2C">2c</A> Trost BM. Toste FD. Pinkerton AB. Chem. Rev.  2001,  101:  2067 

<A NAME="RU04207ST-2D">2d</A> Aubert C. Buisine O. Malacria M. Chem. Rev.  2002,  102:  813 

For examples, see:

<A NAME="RU04207ST-3A">3a</A> Kablaoui NM. Buchwald SL. J. Am. Chem. Soc.  1996,  118:  3182 

<A NAME="RU04207ST-3B">3b</A> Kablaoui NM. Hick FA. Buchwald SL. J. Am. Chem. Soc.  1997,  119:  4424 

<A NAME="RU04207ST-3C">3c</A> Mandal SM. Amin SR. Crowe WE. J. Am. Chem. Soc.  2001,  123:  6457 

<A NAME="RU04207ST-3D">3d</A> Ogoshi S. Oka M. Kurosawa H. J. Am. Chem. Soc.  2004,  126:  11802 

For reviews, see:

<A NAME="RU04207ST-4A">4a</A> Zimmer R. Dinesh CU. Nandann E. Khan FA. Chem. Rev.  2000,  100:  3067 

<A NAME="RU04207ST-4B">4b</A> Ma S. In Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1:  Negishi E. Wiley; New York: 2002.  p.1491-1521  

<A NAME="RU04207ST-4C">4c</A> Trost BM. Acc. Chem. Res.  2002,  35:  695 

<A NAME="RU04207ST-4D">4d</A> Ma S. Eur. J. Org. Chem.  2004,  1175 

<A NAME="RU04207ST-5">5</A> Mandai T. In Modern Allene Chemistry   Vol. 2:  Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.925-972  

<A NAME="RU04207ST-6A">6a</A> Yu C.-M. Youn J. Lee M.-K. Org. Lett.  2005,  7:  3733 

<A NAME="RU04207ST-6B">6b</A> Yu C.-M. Hong Y.-T. Yoon S.-K. Lee J. Synlett  2004,  1695 

<A NAME="RU04207ST-6C">6c</A> Yu C.-M. Hong Y.-T. Lee J. J. Org. Chem.  2004,  69:  8506 

<A NAME="RU04207ST-7A">7a</A> Yu C.-M. Youn J. Jung J. Angew. Chem. Int. Ed.  2006,  45:  1553 

<A NAME="RU04207ST-7B">7b</A> Yu C.-M. Youn J. Jung H.-K. Bull. Korean Chem. Soc.  2006,  27:  463 

<A NAME="RU04207ST-7C">7c</A> Yu C.-M. Kim C. Kweon J.-H. Chem. Commun.  2004,  2494 

<A NAME="RU04207ST-7D">7d</A> Kang S. Hong Y.-T. Lee J.-H. Kim W.-Y. Lee I. Yu C.-M. Org. Lett.  2003,  5:  2813 

<A NAME="RU04207ST-8">8</A> Kang S.-K. Kim K.-J. Hong Y.-T. Angew. Chem. Int. Ed.  2002,  41:  1584 

For reviews, see:

<A NAME="RU04207ST-9A">9a</A> Bloch R. Chem. Rev.  1998,  98:  1407 

<A NAME="RU04207ST-9B">9b</A> Kobayashi S. Ishitani H. Chem. Rev.  1999,  99:  1069 

<A NAME="RU04207ST-10A">10a</A> Morimoto T. Chatani N. Murai S. J. Am. Chem. Soc.  1999,  121:  1758 

<A NAME="RU04207ST-10B">10b</A> Chatani N. Morimoto T. Kamitani A. Fukumoto S. Murai S. J. Orgnomet. Chem.  1999,  579:  177 

For cyclization mediated by Mo, see:

<A NAME="RU04207ST-11A">11a</A> Adrio J. Carretero JC. J. Am. Chem. Soc.  2007,  129:  778 

<A NAME="RU04207ST-11B">11b</A> Brummond KM. Curran DP. Mitasev B. Fischer S. J. Org. Chem.  2005,  70:  1745 

<A NAME="RU04207ST-11C">11c</A> Cao H. Van Ornui SG. Deschamps J. Flippen-Anderson J. Laib F. Cook JM. J. Am. Chem. Soc.  2005,  127:  933 

<A NAME="RU04207ST-12">12</A>

The crystallographic data for the structure of 4b has been deposited at the Cambridge Crystallographic Data Centre (CCDC 645332).

<A NAME="RU04207ST-13">13</A>

4a: ¹H NMR (500 MHz, CDCl₃): δ = 3.57 (dd, J = 4.50, 10.68 Hz, 1 H), 3.71 (m, 1 H), 3.97 (dd, J = 7.31, 8.99 Hz, 1 H), 4.04 (dd, J = 2.81, 8.99 Hz, 1 H), 4.15 (d, J = 10.68 Hz, 1 H), 4.53 (ddd, J = 1.12, 4.50, 7.31 Hz, 1 H), 5.63 (d, J = 2.40 Hz, 1 H), 6.29 (d, J = 2.40 Hz, 1 H), 7.80-7.90 (m, 2 H), 7.91-7.97 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 41.9, 62.9, 71.6, 75.6, 121.6, 124.5, 124.7, 130.1, 130.5, 135.0, 135.1, 139.1, 164.7, 164.9, 165.1. 4b: ¹H NMR (500 MHz, CDCl₃): δ = 2.44 (s, 3 H), 3.25 (m, 2 H), 3.55 (m, 2 H), 3.66 (m, 1 H), 4.47 (ddd, J = 2.25, 5.62, 8.15 Hz, 1 H), 5.56 (d, J = 2.40 Hz, 1 H), 6.22 (d, J = 2.40 Hz, 1 H), 7.35 (m, 2 H), 7.75 (m, 2 H), 7.82 (m, 2 H), 7.91 (m, 1 H), 7.95 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.8, 40.2, 52.2, 53.9, 60.7, 122.2, 124.3, 124.7, 128.3, 130.0, 130.1, 130.2, 132.8, 135.1, 135.3, 137.7, 144.4, 164.5, 164.7, 164.9. 4c: ¹H NMR (500 MHz, CDCl₃): δ = 1.25 (t, J = 7.03 Hz, 6 H), 2.45 (m, 2 H), 2.69 (m, 2 H), 3.69 (m, 1 H), 4.12 (m, 4 H), 4.50 (m, 1 H), 5.57 (d, J = 2.40 Hz, 1 H), 6.63 (d, J = 2.40 Hz, 1 H), 7.80 (m, 2 H), 7.91 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 14.2, 36.7, 40.1, 40.6, 61.0, 61.5, 61.8, 62.1, 62.2, 120.7, 124.1, 124.4, 130.4, 130.7, 135.1, 140.2, 156.6, 164.5, 164.9, 165.2, 170.7, 171.8. 4d: ¹H NMR (500 MHz, CDCl₃): δ = 1.52 (m, 1 H), 1.73 (m, 1 H), 1.84 (m, 1 H), 1.91 (m, 2 H), 2.02 (m, 1 H), 3.51 (m, 1 H), 4.42 (m, 1 H), 5.54 (d, J = 2.40 Hz, 1 H), 6.20 (d, J = 2.40 Hz, 1 H), 7.80 (m, 2 H), 7.91 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 23.5, 31.4, 35.6, 41.0, 62.9, 116.5, 120.0, 124.2, 124.4, 130.5, 134.1, 135.0, 141.9, 155.3, 165.2, 165.9. 4e: ¹H NMR (500 MHz, CDCl₃): δ = 1.50 (d, J = 6.30 Hz, 3 H), 2.44 (s, 3 H), 3.30 (m, 1 H), 3.51 (m, 1 H), 3.61 (m, 1 H), 4.12 (m, 1 H), 4.50 (m, 1 H), 5.46 (d, J = 2.40 Hz, 1 H), 6.00 (d, J = 2.40 Hz, 1 H), 7.16-7.35 (m, 2 H), 7.81-7.97 (m, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 16.6, 20.3, 45.3, 51.0, 60.0, 61.7, 116.6, 121.5, 123.5, 124.4, 124.6, 127.7, 128.1, 130.0, 130.1, 134.8, 135.2, 135.4, 136.9, 144.1, 164.9, 164.9. 4f: ¹H NMR (500 MHz, CDCl₃): δ = 1.48 (s, 3 H), 2.45 (s, 3 H), 3.03 (m, 1 H), 3.10 (m, 2 H), 3.63 (m, 2 H), 5.53 (d, J = 2.40 Hz, 1 H), 6.20 (m, 1 H), 7.27-7.43 (m, 2 H), 7.65-7.97 (m, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.9, 23.7, 47.7, 54.3, 58.0, 68.8, 122.1, 124.5, 124.6, 128.3, 130.1, 130.2, 132.2, 135.3, 135.4, 138.0, 144.4, 163.8, 165.4, 165.5. 4g: ¹H NMR (500 MHz, CDCl₃): δ = 1.85 (dq, J = 2.9, 14.7 Hz, 1 H), 2.04 (m, 1 H), 2.45 (s, 3 H), 2.61 (dd, J = 10.7, 12.7 Hz, 1 H), 2.94 (ddd, J = 2.9, 11.7, 11.7 Hz, 1 H), 3.41 (m, 1 H), 3.55 (m, 1 H), 3.75 (ddd, J = 2.0, 6.8, 12.7 Hz, 1 H), 4.15 (m, 1 H), 5.62 (s, 1 H), 6.24 (s, 1 H), 7.35 (d, J = 7.8 Hz, 2 H), 7.66 (d, J = 7.8 Hz, 2 H), 7.80 (m, 2 H), 7.88 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 25.3, 29.9, 36.9, 41.3, 46.7, 54.2, 121.7, 124.1, 124.4, 124.4, 127.4, 127.7, 130.0, 130.0, 130.3, 133.9, 135.0, 135.2, 137.7, 144.2, 164.6, 165.4, 166.4.