Platinum-Catalyzed Tandem Cyclization-Nazarov Cylization Reactions: An Easy Access to Complex Carbocyclic Molecules from 2-Alkenyl-(1′-hydroxyl-4-en-2-ynyl)benzenes

Abstract

In the presence of PtCl₂/CO catalyst, 2-alkenyl-(1′-hydroxyl-4-en-2-ynyl)benzenes undergo a tandem electrophilic 6-exo-dig cyclization-Nazarov cyclization sequence to give 1H-cyclopenta[a]naphthalenes efficiently and regioselectively.

alcohols - alkynes - carbenoids - catalysis - tandem reactions

References and Notes

<A NAME="RY01507ST-1A">1a</A> Ho TL. In Tandem Organic Reactions   New York; Wiley: 1992. 

<A NAME="RY01507ST-1B">1b</A> Nicolaou KC. Yue EW. Oshima T. In The New Chemistry   Hall N. Cambridge University Press; Cambridge: 2001.  p.168 

<A NAME="RY01507ST-1C">1c</A> Tietze LF. Hautner F. In Stimulating Concepts in Chemistry   Vögtle F. Stoddart JF. Shibasaki M. Wiley-VCH; Weinheim: 2000.  p.38 

<A NAME="RY01507ST-1D">1d</A> Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Engl.  1993,  32:  131 ; Angew. Chem. 1993, 105, 103

<A NAME="RY01507ST-1E">1e</A> Tietze LF. Chem. Rev.  1996,  96:  115 

<A NAME="RY01507ST-2A">2a</A> Corkey BK. Toste FD. J. Am. Chem. Soc.  2007,  129:  2764 

<A NAME="RY01507ST-2B">2b</A> Trost BM. Krische MJ. Synlett  1998,  1 

<A NAME="RY01507ST-2C">2c</A> Aubert C. Buisine O. Malacria M. Chem. Rev.  2002,  102:  813 

<A NAME="RY01507ST-2D">2d</A> Lloyd-Jones GC. Org. Biomol. Chem.  2003,  1:  215 

For recent reviews for gold and platinum catalysis, see:

<A NAME="RY01507ST-3A">3a</A> Fürstner A. Davies PW. Angew. Chem. Int. Ed.  2007,  46:  3410 

<A NAME="RY01507ST-3B">3b</A> Gorin DJ. Toste FD. Nature (London)  2007,  446:  395 

<A NAME="RY01507ST-3C">3c</A> Jimenez-Nunez E. Echavarren AM. Chem. Commun.  2007,  333 

<A NAME="RY01507ST-3D">3d</A> Zhang L. Sun J. Kozmin SA. Adv. Synth. Catal.  2006,  348:  2271 

<A NAME="RY01507ST-3E">3e</A> Hashmi ASH. Angew. Chem. Int. Ed.  2005,  44:  6990 

For gold-catalyzed cycloisomerizations of enynes, see selected examples:

<A NAME="RY01507ST-4A">4a</A> Nieto-Oberhuber C. Munoz PM. Bunuel E. Nevado C. Cardenas DJ. Echavarren AM. Angew. Chem. Int. Ed.  2004,  43:  2402 

<A NAME="RY01507ST-4B">4b</A> Luzung MR. Markham JP. Toste FD. J. Am. Chem. Soc.  2004,  126:  10858 

<A NAME="RY01507ST-4C">4c</A> Horino Y. Luzung MR. Toste FD. J. Am. Chem. Soc.  2006,  128:  11364 

<A NAME="RY01507ST-4D">4d</A> Zhang L. Kozmin SA. J. Am. Chem. Soc.  2004,  126:  11806 

<A NAME="RY01507ST-4E">4e</A> Zhang L. J. Am. Chem. Soc.  2005,  127:  16804 

<A NAME="RY01507ST-4F">4f</A> Sun J. Conley MP. Zhang L. Kozmin SA. J. Am. Chem. Soc.  2006,  128:  9705 

<A NAME="RY01507ST-4G">4g</A> Buzas A. Gagosz F. J. Am. Chem. Soc.  2006,  128:  12614 

<A NAME="RY01507ST-4H">4h</A> Kirsch SF. Binder JT. Crone B. Duschek A. Haug TT. Liébert C. Menz H. Angew. Chem. Int. Ed.  2007,  46:  2310 

For PtCl₂-catalyzed cycloisomerization of enynes, see selected examples:

<A NAME="RY01507ST-5A">5a</A> Chatani N. Furukawa N. Sakurai H. Murai S. Organometallics  1996,  15:  901 

<A NAME="RY01507ST-5B">5b</A> Trost BM. Doherty GA. J. Am. Chem. Soc.  2000,  122:  3801 

<A NAME="RY01507ST-5C">5c</A> Fürstner A. Szillat H. Stelzer F. J. Am. Chem. Soc.  2000,  122:  6785 

<A NAME="RY01507ST-5D">5d</A> Méndez M. Munoz MP. Nevado C. Cardenas DJ. Echavarren AM. J. Am. Chem. Soc.  2001,  123:  10511 

<A NAME="RY01507ST-5E">5e</A> Mamane V. Gress T. Krause H. Fürstner A. J. Am. Chem. Soc.  2004,  126:  8654 

<A NAME="RY01507ST-5F">5f</A> Harrak Y. Blaszykowski C. Bernard M. Cariou K. Mainetti E. Mouriès V. Dhimane A.-L. Fensterbank L. Malacria M. J. Am. Chem. Soc.  2004,  126:  8656 

<A NAME="RY01507ST-5G">5g</A> Blaszykowski C. Harrak Y. Goncalves M.-H. Cloarec J.-M. Dhimane A.-L. Fensterbank L. Malacria M. Org. Lett.  2004,  6:  3771 

<A NAME="RY01507ST-5H">5h</A> Soriano E. Marco-Contelles J. J. Org. Chem.  2005,  70:  9345 

<A NAME="RY01507ST-5I">5i</A> Harrison TJ. Patrick BO. Dake GR. Org. Lett.  2007,  9:  367 

For cycloisomerization of enynes by other metals, see selected examples:

<A NAME="RY01507ST-6A">6a</A> Trost BM. Hashmi ASK. Angew. Chem., Int. Ed. Engl.  1993,  32:  1085 

<A NAME="RY01507ST-6B">6b</A> Goeke A. Sawamura M. Kuwano R. Ito Y. Angew. Chem., Int. Ed. Engl.  1996,  35:  662 

<A NAME="RY01507ST-6C">6c</A> Wender PA. Sperandio D. J. Org. Chem.  1998,  63:  4164 

<A NAME="RY01507ST-6D">6d</A> Chatani N. Kataoka K. Murai S. Furukawa N. Seki Y. J. Am. Chem. Soc.  1998,  120:  9104 

<A NAME="RY01507ST-6E">6e</A> Trost BM. Toste FD. J. Am. Chem. Soc.  2000,  122:  714 

<A NAME="RY01507ST-6F">6f</A> Sémeril D. Cléran M. Bruneau C. Dixneuf PH. Adv. Synth. Catal.  2001,  343:  184 

<A NAME="RY01507ST-6G">6g</A> Chatani N. Inoue H. Kotsuma T. Murai S. J. Am. Chem. Soc.  2002,  124:  10294 

<A NAME="RY01507ST-7A">7a</A> Fürstner A. Davies PW. Gress T. J. Am. Chem. Soc.  2005,  127:  8244 

<A NAME="RY01507ST-7B">7b</A> Fürstner A. Stelzer F. J. Am. Chem. Soc.  2001,  123:  11863 

<A NAME="RY01507ST-7C">7c</A> Lin M.-Y. Das A. J. Am. Chem. Soc.  2006,  128:  9340 

<A NAME="RY01507ST-7D">7d</A> Tang J.-M. Bhunia S. Sohel SMA. Lin M.-Y. Liao H.-Y. Datta S. Das A. Liu R.-S. J. Am. Chem. Soc.  2007,  129:  15677 

<A NAME="RY01507ST-8">8</A> Taduri BP. Sohel SMA. Cheng H.-M. Lin G.-Y. Liu R.-S. Chem. Commun.  2007,  2530 

Selected examples:

<A NAME="RY01507ST-9A">9a</A> Nazarov IN. Torgov IB. Terekhova LN. Izv. Akad. Nauk. SSSR Otd. Khim. Nauk  1942,  200 

<A NAME="RY01507ST-9B">9b</A> Janka M. He W. Haedicke IE. Fronczek FR. Frontier AJ. Eisenberg R. J. Am. Chem. Soc.  2006,  128:  5312 

<A NAME="RY01507ST-9C">9c</A> Malona JA. Colbourne JM. Frontier AJ. Org. Lett.  2006,  8:  5661 

<A NAME="RY01507ST-9D">9d</A> Lee JH. Toste FD. Angew. Chem. Int. Ed.  2007,  46:  912 

<A NAME="RY01507ST-9E">9e</A> Zhang L. Wang S. J. Am. Chem. Soc.  2006,  128:  1442 

<A NAME="RY01507ST-9F">9f</A> He W. Sun X. Frontier AJ. J. Am. Chem. Soc.  2003,  125:  14278 

<A NAME="RY01507ST-9G">9g</A> Bee C. Leclerc E. Tius M. Org. Lett.  2003,  5:  4927 

<A NAME="RY01507ST-10A">10a</A> Milstein D. Stille JK. J. Am. Chem. Soc.  1979,  101:  4992 

<A NAME="RY01507ST-10B">10b</A> Scott WJ. Crisp GT. Stille JK. J. Am. Chem. Soc.  1984,  106:  4630 

<A NAME="RY01507ST-10C">10c</A> Stille JK. Angew. Chem., Int. Ed. Engl.  1986,  25:  508 ; Angew. Chem. 1986, 98, 504

<A NAME="RY01507ST-10D">10d</A> Farina V. In Comprehensive Organometallic Chemistry II   Vol. 12:  Abel EW. Stone FGA. Wilkinson G. Pergamon; Oxford: 1995. 

<A NAME="RY01507ST-10E">10e</A> Espinet P. Echavarren AM. Angew. Chem. Int. Ed.  2004,  43:  4704 

<A NAME="RY01507ST-10F">10f</A> Jung ME. Ho D. Chu HV. Org. Lett.  2005,  7:  1649 

For the PtCl₂/CO catalysis, see ref. 7a and:

<A NAME="RY01507ST-11A">11a</A> Fürstner A. Aïssa C. J. Am. Chem. Soc.  2006,  128:  6306 

<A NAME="RY01507ST-11B">11b</A> Fürstner A. Davies PW. J. Am. Chem. Soc.  2005,  127:  15024 

<A NAME="RY01507ST-12">12</A> Norman ROC. Coxon JM. In Principles of Organic Synthesis   3rd ed.:  Blackie Academic and Professional; Glasgow: 1993.  p.68 

<A NAME="RY01507ST-13">13</A>

Magnesium oxide was added to remove Brønsted acid given from PtCl₂ and water in this system. We envisage that Brønsted may enhance the transformation of alcohol substrate 13 into indene derivative 24 through a simple Nazarov cyclization as depicted in Scheme [6] .

<A NAME="RY01507ST-14">14</A>

See ref. 7d for the formation mechanism of the ketone product 36.

<A NAME="RY01507ST-15">15</A>

Typical Procedure for the Synthesis of 4-Methyl-1-[2-(prop-1-en-2-yl)phenyl]pent-4-en-2-yn-1-ol (3)
To a THF (15 mL) solution of 2-bromobenzaldehyde (1.00 g, 5.40 mmol) was added tributyl(prop-1-en-2-yl)stannane (1.87 g, 1.05 mmol), Pd(PPh₃)₄ (311 mg, 0.27 mmol), CuCl (0.80 g, 8.10 mmol) and LiBr (0.7 g, 8.10 mmol); the mixture was heated in a sealed tube at 60 °C for 8 h. The resulting solution was concentrated under reduced pressure, and the residues were eluted through a silica column (hexane-EtOAc, 98:2) to afford 2-(prop-1-en-2-yl)benz-aldehyde (639 mg, 4.37 mmol, 81%) as colorless oil. To a THF (8 mL) solution of 2-methylbut-1-en-3-yne (0.29 g, 4.45 mmol) was slowly added n-BuLi (1.6 mL, 2.5 M in hexane) at -78 °C; the solution was stirred for 30 min at -78 °C before addition of a THF solution (2 mL) of 2-(prop-1-en-2-yl)benzaldehyde (0.50 g, 3.42 mmol). After 30 min, to this solution was added H₂O (3 mL); the solution was extracted with EtOAc, and concentrated to afford crude alcohol. The crude product was eluted through a silica column (hexane-EtOAc, 5:1) to afford substrate 3 (640 mg, 3.01 mmol, 88%) as a light yellow oil.

<A NAME="RY01507ST-16">16</A>

Typical Procedure for the 6- exo - dig -Nazarov tandem cyclization of 4-Methyl-1-(2-prop-1-en-2-yl)phenylpent-4-en-2-yn-1-ol(1) to 1,5-Dimethyl-1 H -cyclopenta[ a ]naphthalene (4)
A long tube containing PtCl₂ (6.3 mg, 0.023 mmol) was evacuated and backfilled with CO. After repeating this procedure twice, the tube was charged with alcohol substrate 3 (100 mg, 0.472 mmol) and dry THF (2 mL). The resulting mixture was stirred at 23 °C for 20 h. The solution was concentrated and eluted through a silica column (hexane) to give compound 4 (81 mg, 0.417 mmol, 89%) as viscous oil.

<A NAME="RY01507ST-17">17</A>

4-Methyl-1-[2-(prop-1-en-2-yl)phenyl])pent-4-en-2-yn-1-ol (3)
IR (neat): 3654 (m), 1624 (m), 1610 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.76 (d, J = 7.0 Hz, 1 H), 7.33-7.29 (m, 2 H), 7.17 (d, J = 7.0 Hz, 1 H), 5.79 (s, 1 H), 5.32 (s, 1 H), 5.25 (s, 1 H), 5.24 (s, 1 H), 4.99 (s, 1 H), 2.12 (s, 3 H), 1.89 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.0, 142.4, 137.5, 128.0, 127.8, 127.4, 127.1, 126.1, 122.1, 116.0, 88.7, 87.1, 61.8, 25.3, 23.1. HRMS: m/z calcd for C₁₅H₁₆O: 212.1201; found: 212.1204.

<A NAME="RY01507ST-18">18</A>

1,5-Dimethyl-1 H -cyclopenta[ a ]naphthalene (4)
IR (neat): 1598 (m) cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.96 (d, J = 8.0 Hz, 1 H), 7.68 (d, J = 8.0 Hz, 1 H), 7.44 (t, J = 8.0 Hz, 1 H), 7.36 (t, J = 8.0 Hz, 1 H), 7.31 (s, 1 H), 6.53 (s, 1 H), 3.58 (s, 2 H), 2.69 (s, 3 H), 2.22 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.6, 142.9, 137.2, 133.0, 129.9, 129.8, 127.6, 125.6, 125.1, 123.7, 123.6, 120.8, 41.5, 19.7, 16.8. HRMS: m/z calcd for C₁₅H₁₄: 194.1096; found: 194.1092.