Reactivity and Utility of Allenylphosphonates: Formation of a Novel Hydroperoxide and Propargylic Alcohol and Facile Thiol Addition under Catalyst-Free, Solvent-Free Conditions

Abstract

2-(Propa-1,2-dienyl)-, 2-(buta-1,2-dienyl)-, and 2-(3-methylbuta-1,2-dienyl)-substituted 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 1a-c react readily upon heating with thiols under catalyst-free, base-free, and solvent-free conditions to give sulfanyl-substituted phosphonates. The reaction undergoes to essential completion within 15 minutes under microwave radiation. While 1a,b react with 4-chlorothiophenol to afford both 2-[2-(4-chlorophenylsulfanyl)prop-1-enyl]- 12 and 2-[2-(4-chlorophenylsulfanyl)prop-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 13, 1c gives 2-[2-(4-chlorophenylsulfanyl)-3-methylbut-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (13d) regioselectively. Molecular oxygen undergoes a novel reaction with the allene 1c to give propargylic alcohol 2-(3-hydroxy-3-methylbut-1-ynyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (16) via the corresponding hydroperoxide; the structures of these were confirmed by X-ray crystallography. The synthetic utility of the sulfanyl-substituted allyphosphonate 13d in the Horner-Wadsworth-Emmons reaction to afford synthetically valuable sulfanyl-substituted buta-1,3-dienes and a conjugated triene is demonstrated.

Key words

allenes - thiol addition - oxygenation - Horner-Wadsworth­-Emmons reaction - allenylphosphonates

References

• 1a Yamamoto Y. Radhakrishnan U. Chem. Soc. Rev.  1999,  28:  199 
• 1b Zimmer R. Dinesh CU. Nandanan E. Khan FA. Chem. Rev.  2000,  100:  3067 
• 1c Lu X. Zhang C. Xu Z. Acc. Chem. Res.  2001,  34:  535 
• 1d Bates RW. Satcharoen V. Chem. Soc. Rev.  2002,  31:  12 
• 1e . Xiong H. Hsung RP. Acc. Chem. Res.  2003,  36:  773 
• 1f Ma S. Acc. Chem. Res.  2003,  36:  701 
• 1g Hoffmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 
• 1h Ma S. Chem. Rev.  2005,  105:  2829 
• 2a Chang H.-M. Cheng CH. J. Org. Chem.  2000,  65:  1767 
• 2b Huang T.-H. Chang H.-M. Wu MY. Cheng CH. J. Org. Chem.  2002,  67:  99 
• 2c Friese JC. Krause S. Schäfer HJ. Tetrahedron Lett.  2002,  43:  2683 
• 2d Chang Wu M.-S. Rayabarapu DK. Cheng CH. J. Am. Chem. Soc.  2003,  125:  12426 
• 2e Oh CH. Ahn TW. Raghava Reddy V. Chem. Commun.  2003,  2622 
• 2f Ma S. Jiao N. Ye L. Chem. Eur. J.  2003,  9:  6049 
• 2g Fürmeier S. Lau MML. Jie MSFLK. Lützen A. Metzger JO. Eur. J. Org. Chem.  2003,  4874 
• 2h Fleming SA. Carroll SM. Hirshi J. Liu R. Pace JL. Redd JT. Tetrahedron Lett.  2004,  45:  3341 
• 2i Hopkins CD. Malinakova HC. Org. Lett.  2004,  6:  2221 
• 2j Silvetri MA. Bromfield DC. Lepore SE. J. Org. Chem.  2005,  70:  8239 
• 2k Fu C. Ma S. Org. Lett.  2005,  7:  1707 
• 3a Schuster HF. Coppola GM. Allenes in Organic Synthesis   John Wiley & Sons; New York: 1984.  p.247-252  
• 3b Alabugin IV. Brei VK. Russ. Chem. Rev. (Engl. Transl.)  1997,  66:  205 
• 3c Patois C. Richard L. Savignac P. J. Chem. Soc., Perkin Trans. 1  1990,  1577 
• 3d Zapata AJ. Gu Y. Hammond GB. J. Org. Chem.  2000,  65:  227 
• 3e Zhao CQ. Han LB. Tanaka M. Organometallics  2000,  19:  4196 
• 3f Rubin M. Markov J. Chuprakov S. Wink DJ. Gevorgyan V. J. Org. Chem.  2003,  68:  6251 
• 3g Wu Z. Huang X. Synlett  2005,  526 
• 3h Nishimura T. Hirabayashi S. Hayashi T. J. Am. Chem. Soc.  2006,  126:  2556 
• 3i Ma S. Guo H. Yu F. J. Org. Chem.  2006,  71:  6634 
• 3j Chakravarty M. Kumara Swamy KC. J. Org. Chem.  2006,  71:  9128 
• 4a Palacios F. Aparicio D. García J. Tetrahedron  1996,  52:  9609 
• 4b Zapata AJ. Gu Y. Hammond GB. J. Org. Chem.  2000,  65:  227 
• 4c Johnson JS. Bergman RG. J. Am. Chem. Soc.  2001,  123:  2923 
• 5 Kumara Swamy KC. Balaraman E. Satish Kumar N. Tetrahedron  2006,  62:  10152 
• 6a Lu X. Zhang C. Xu Z. Acc. Chem. Res.  2001,  34:  535 
• 6b Zhang C. Lu X. Synlett  1995,  645 
• 7a Jacobs TL. Illingworth GE. J. Org. Chem.  1963,  28:  2692 
• 7b Pasto DJ. Warren SE. Morrison MA. J. Org. Chem.  1981,  46:  2837 
• 7c Ogawa A. Kawakami J.-i. Sonoda N. Hirao T. J. Org. Chem.  1996,  61:  4161 
• 8a Pudovik AN. Khusainova NG. Abdulina TA. J. Gen. Chem. USSR (Engl. Transl.)  1967,  37:  809 
• 8b Khusainova NG. Mostovaya OA. Berdnikov EA. Efremov YY. Sharafutdinova DR. Cherkasov RA. Russ. Chem. Bull. (Engl. Transl.)  2004,  53:  2253 
• 8c Khusainova NG. Mostovaya OA. Berdnikov EA. Cherkasov RA. Russ. Chem. Bull. (Engl. Transl.)  2003,  52:  1033 
• 9a Muthiah C. Praveen Kumar K. Aruna Mani C. Kumara Swamy KC. J. Org. Chem.  2000,  65:  3733 
• 9b Muthiah C. Senthil Kumar K. Vittal JJ. Kumara Swamy KC. Synlett  2002,  1787 
• 9c Kumaraswamy S. Kommana P. Satish Kumar N. Kumara Swamy KC. Chem. Commun.  2002,  40 
• 9d Chakravarty M. Srinivas B. Muthiah C. Kumara Swamy KC. Synthesis  2003,  2368 
• 9e Balaraman E. Kumara Swamy KC. Synthesis  2004,  3037 
• 9f Satish Kumar N. Praveen Kumar K. Pavan Kumar KVP. Kommana P. Vittal JJ. Kumara Swamy KC. J. Org. Chem.  2004,  69:  1880 
• 9g Kumara Swamy KC. Kumaraswamy S. Senthil Kumar K. Muthiah C. Tetrahedron Lett.  2005,  46:  3347 
• 9h Kumara Swamy KC. Praveen Kumar K. Bhuvan Kumar NN. J. Org. Chem.  2006,  71:  1002 
• 9i Kumara Swamy KC. Satish Kumar N. Acc. Chem. Res.  2006,  39:  324 
• 9j Bhuvan Kumar NN. Chakravarty M. Kumara Swamy KC. New J. Chem.  2006,  30:  1614 
• 13 Sander W. Patyk A. Angew. Chem., Int. Ed. Engl.  1987,  26:  475 ; and references cited therein
• 14 Such trienes are perhaps useful in cyclization reactions, see: Murahashi T. Nakashima H. Nagai T. Mino Y. Okuno T. Jalil MA. Kurosawa H. J. Am. Chem. Soc.  2006,  128:  4377 ; and references cited therein
• 15 Zhijie N. Padwa A. Synlett  1992,  869 
• 16a Organic Chemistry of Sulfur   Oae S. Plenum; New York: 1977. 
• 16b Bernardi F. Mangini E. Organic Sulfur Chemistry: Theoretical and Experimental Advances   Elsevier; Amsterdam: 1985. 
• 18 Perrin DD. Armarego WLF. Perrin DR. Purification of Laboratory Chemicals   Pergamon; Oxford: 1986. 
• 19a Satish Kumar N. Ph.D. Thesis   University of Hyderabad; India: 2004. 
• 19b Guillemin JC. Savignac P. Denis JM. Inorg. Chem.  1991,  30:  2170 
• 20a Sheldrick GM. SADABS, Siemens Area Detector Absorption Correction   University of Göttingen; Germany: 1996. 
• 20b Sheldrick GM. SHELXTL NT Crystal Structure Analysis Package   version 5.10:  Bruker AXS, Analytical X-ray System; WI USA: 1999. 

10

The ¹H NMR spectrum of this mixture showed peaks at δ = 3.40 (d, J = 22.0 Hz), in addition to those for 12a and 1a. There was also an additional minor peak in the initial stages in the ³¹P NMR at δ = 23.9 (unassigned).

11

Compound 15 was more difficult to obtain in a pure form, probably because of conversion into 16.

12

When we tried to separate this compound from 5,5-diethyl-2-(3-methylbuta-1,2-dienyl)-1,3,2-dioxaphosphinane 2-oxide using column chromatography, a small quantity of an additional species [δ(P) -12.2] was noticed in a few fractions.

17

IR (KBr): 3399, 2928, 1570, 1335, 1206, 1057, 1005 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 0.99 and 1.10 (2 s, 6 H, 2 CH ₃), 2.01-2.06 [2 m due to coupling to phosphorus and CH₂ with J <5.0 Hz, 6 H, =C(CH ₃)₂], 3.34 (dd, J ˜4.0 Hz, J ˜20.6 Hz, 2 H, PCH ₂), 3.79-4.95 (m, 9 H, CH ₂OH, CHCH₂OH, 2 CHOH, OCH ₂), 5.90 (d, J ˜7.0 Hz, OCHN of ribose), 8.13 (s, 1 H, nucleobase-H), 8.62 (s, 1 H, Nucleobase-H); LC-MS showed a peak at m/z 503.