Sodium Hypophosphite Decomplexation of Acetylenebiscobalthexacarbonyls to cis-Olefins

Abstract

Reductive decomplexation of acetylenebiscobalthexa-carbonyl is best achieved with tri-n-butyltin hydride. Instead of this toxic reagent, sodium hypophosphite monohydrate has proved to be a safe, effective, and economical reagent for such a reductive decomplexation of biscobalthexacarbonyl acetylenes into the corresponding cis-olefins.

Key words

acetylenebiscobalthexacarbonyl - sodium hypophosphite - reductive decomplexation - Nicholas reaction - ciguatoxin

References

• 1a Saha M. Baphy B. Nicholas KM. Tetrahedron Lett.  1986,  27:  915 
• 1b Harrington PJ. Transition Metals in Total Synthesis   John Wiley; New York: 1990.  p.241 
• 1c Jamison TF. Shambayati S. Crowe WE. Shreiber SL. J. Am. Chem. Soc.  1994,  116:  5055 
• 1d Mukai C. Kadota O. Hanaoka M. J. Org. Chem.  1995,  60:  5910 
• 2a Nicholas KM. Pettit R. Tetrahedron Lett.  1971,  3475 
• 2b Seyferth D. Nestle MO. Wehman AT. J. Am. Chem. Soc.  1975,  97:  7417 
• 3a Connor RE. Nicholas KM. J. Organomet. Chem.  1977,  125:  C45 
• 3b Nicholas KM. Acc. Chem. Res.  1987,  20:  207 
• 4a Khand IU. Knox GR. Pauson PL. Watts WE. Foreman MI. J. Chem. Soc., Perkin Trans. 1  1973,  977 
• 4b Pauson PL. Tetrahedron  1985,  41:  5855 
• 4c Shore NE. In Comprehensive Organometallic Chemistry II   Vol. 12:  Hegedus LS. Pergamon Elsevier; Amsterdam: 1995.  Chap 7.2. p.703 
• 4d Geis O. Schmalz H.-G. Angew. Chem. Int. Ed.  1998,  37:  911 
• 5a Shvo Y. Hazum EJ. J. Chem. Soc., Chem. Commun.  1974,  336 
• 5b Magnus P. Becker DP. J. Chem. Soc., Chem. Commun.  1985,  640 
• 5c Schreiber SL. Sammakia T. Crowe WE. J. Am. Chem. Soc.  1986,  108:  3128 
• 5d Davis DS. Shadinger SC. Tetrahedron Lett.  1999,  44:  7749 
• 6a Jones GB. Huber RS. Mathews JE. J. Chem. Soc., Chem. Commun.  1995,  1791 
• 6b Jones GB. Wright JM. Rush TM. Ploude GW. Kelton TF. Mathews JE. Huber RS. Davidson JP. J. Org. Chem.  1997,  62:  9379 
• 7a Nakamura T. Matsui T. Tanino K. Kuwajima I. J. Org. Chem.  1997,  62:  3032 
• 7b Iwasawa N. Satoh H. J. Am. Chem. Soc.  1999,  121:  7951 
• 8a Hirama M. Oishi T. Uehara H. Inoue M. Maruyama M. Oguri H. Satake M. Science  2001,  294:  1904 
• 8b Takakura H. Noguchi K. Sasaki M. Tachibana K. Angew. Chem. Int. Ed.  2001,  40:  1090 
• 8c Fujiwara K. Takaoka D. Kusumi K. Kawai K. Murai A. Synlett  2001,  691 
• 8d Eriksson L. Guy S. Perlmutter P. J. Org. Chem.  1999,  64:  8396 
• 8e Leeuwenburgh MA. Kulker C. Overkleeft HS. van der Marel GA. van Boom JH. Synlett  1999,  1945 
• 8f Ravelo JD. Regueiro A. Roddriguez E. Vera J. Martin JD. Tetrahedron Lett.  1996,  37:  2869 
• 8g Soler MA. Palazon JM. Martin VS. Tetrahedron Lett.  1993,  34:  5471;  and references therein
• 9a Hosokawa S. Isobe M. Synlett  1995,  1179 
• 9b Hosokawa S. Isobe M. Synlett  1996,  351 
• 9c Hosokawa S. Isobe M. J. Org. Chem.  1999,  64:  37 
• 9d Saeeng R. Isobe M. Tetrahedron Lett.  1999,  40:  1911 
• 9e Saeeng R. Isobe M. Heterocycles  2001,  54:  789 
• 9f Kira K. Isobe M. Tetrahedron Lett.  2000,  41:  5951 
• 9g Liu T.-Z. Isobe M. Synlett  2000,  587 
• 9h Liu T.-Z. Li J.-M. Isobe M. Tetrahedron  2000,  56:  5391 
• 9i Kira K. Isobe M. Chem. Lett.  2001,  432 
• 9j Kira K. Isobe M. Tetrahedron Lett.  2001,  42:  2821 
• 9k Kira K. Hamajima A. Isobe M. Tetrahedron  2002,  58:  1875 
• 9l Liu T.-Z. Isobe M. Synlett  2000,  266 
• 9m Liu T.-Z. Li J.-M. Isobe M. Tetrahedron  2000,  56:  10209 
• 10a Scheuer PJ. Takahashi W. Tsutsumi J. Yoshida T. Science  1967,  155:  1267 
• 10b Murata M. Legurand AM. Ishibashi Y. Fukui M. Yasumoto T. J. Am. Chem. Soc.  1990,  112:  4380 
• 10c Satake M. Morohashi A. Oguri H. Oishi T. Hirama M. Harada N. Yasumoto T. J. Am. Chem. Soc.  1997,  119:  11325 
• 10d Yasumoto T. Chem. Rec.  2001,  1:  228 
• 11a Hosokawa S. Isobe M. Tetrahedron Lett.  1998,  39:  2609 
• 11b Isobe M. Nishizawa R. Hosokawa S. Nishikawa T. Chem. Commun.  1998,  2665 
• 11c Shibuya S. Isobe M. Tetrahedron  1998,  54:  6677 
• 11d Kira K. Isobe M. J. Org. Chem., Jpn.  2000,  58:  23 
• 11e Kira K. Isobe M. J. Org.Chem., Jpn.  2000,  58:  99 
• 14a Graham AE. Thomas AV. Yang RC. J. Org. Chem.  2000,  65:  2583 
• 14b Barton DH. Jang DO. Jaszberenyi JC. J. Org. Chem.  1993,  58:  6838 
• 16 Isobe M. Takai S. J. Organomet. Chem.  1999,  589:  122 
• 17 Syambayati S. Crowe WE. Schreiber SL. Tetrahedron Lett.  1990,  31:  5289 

12

Aldrich, 500 g, $ 430 in Japan.

13

WAKO, 500 g, $ 18 in Japan.

15

A reductive decomplexation of 24 with n-Bu₃SnH was successful to give 33, which was trans-olefin. A possible mechanism is shown below (Figure [2] ).

Figure 2

18

Physical data for 29. IR (KBr): 3447, 2925, 2359, 2344, 2094, 2055, 2028, 1734, 1560, 1285, 1144 cm^-1. ¹H NMR (CDCl₃, 400 MHz) δ 1.19 (9 H, s, -OPiv), 1.22 (9 H, s, -OPiv), 1.64 (1 H, dddd, J = 14.5, 9.0, 6.0, 5.0 Hz, H-14), 2.15 (1 H, dddd, J = 14.5, 7.5, 7.5, 2.5 Hz, H-14), 2.84 (1 H, br-s, -OH), 2.87 (1 H, dd, J = 15.5, 9.5 Hz, H-8), 2.94 (1 H, dd, J = 9.0, 9.0 Hz, H-12), 3.29 (1 H, ddd, J = 9.0, 9.0, 2.5 Hz, H-13), 3.35 (3 H, m, -OMe), 3.39 (1 H, ddd, J = 9.5, 9.0, 4.0 Hz, H-9), 3.47-3.60 (2 H, m, H-15), 3.52 (1 H, dd, J = 9.0, 9.0 Hz, H-10), 3.59 (3 H, m, -OMe), 3.59 (1 H, dd, J = 15.5, 4.0 Hz, H-8), 3.64 (1 H, dd, J = 9.0, 9.0 Hz, H-11), 4.09 (1 H, dd, J = 11.5, 7.0 Hz, H-1), 4.29 (1 H, dd, J = 11.5, 3.5 Hz, H-1), 5.06 (1 H, dd, J = 4.5, 1.5 Hz, H-5), 5.58 (1 H, ddd, J = 7.0, 6.5, 3.5 Hz, H-2), 5.86 (1 H, ddd, J = 15.5, 6.5, 1.5 Hz, H-3), 5.96 (1 H, ddd, J = 15.5, 4.5, 1.0 Hz, H-4). ¹³C NMR (CDCl₃, 100 MHz) δ 27.09, 27.11, 29.70, 32.01, 38.67, 38.82, 38.87, 58.53, 60.45, 64.71, 68.95, 70.84, 74.95, 75.02, 77.50, 77.88, 81.10, 82.59, 87.47, 91.78, 99.87, 125.80, 131.89, 177.18, 178.07, 198.74, 199.23, 201.69. ESI Q-TOF MS calcd for C₃₃H₄₃Co₂O₁₅ [M + H]⁺ 797.127, found 797.128. [α]_D ²⁵ +170.0 (c 0.05, CHCl₃).

19

Physical data for 30. IR (KBr): 3448, 2962, 2925, 2360, 2344, 1734, 1718, 1282, 1144, 1108 cm^-1. ¹H NMR (CDCl₃, 400 MHz) δ 1.18 (9 H, s, -OPiv), 1.21 (9 H, s, -OPiv), 1.64 (1 H, dddd, J = 14.0, 9.0, 5.5, 5.5 Hz, H-14), 2.12 (1 H, dddd, J = 14.0, 7.5, 7.5, 3.0 Hz, H-14), 2.32 (1 H, m, H-8), 2.58 (1 H, ddd, J = 15.5, 8.5, 3.5 Hz, H-8), 2.75 (1 H, br-s, -OH), 2.92 (1 H, dd, J = 9.0, 9.0 Hz, H-12), 3.12 (1 H, ddd, J = 10.5, 9.0, 3.5 Hz, H-9), 3.29 (1 H, m, H-13), 3.29 (1 H, dd, J = 9.0, 9.0 Hz, H-10), 3.33 (3 H, s, -OMe), 3.50 (1 H, dd, J = 7.5, 5.5 Hz, H-15), 3.52 (1 H, dd, J = 9.0, 7.5 Hz, H-15), 3.59 (3 H, s, -OMe), 3.64 (1 H, dd, J = 9.0, 9.0 Hz, H-11), 4.09 (1 H, dd, J = 11.5, 7.0 Hz, H-1), 4.27 (1 H, dd, J = 11.5, 3.5 Hz, H-1), 4.50-4.54 (1 H, m, H-5), 5.51 (1 H, ddd, J = 6.5, 6.0, 3.5 Hz, H-2), 5.72 (1 H, ddd, J = 15.5, 6.0, 1.5 Hz, H-3), 5.77 (1 H, ddd, J = 11.0, 4.5, 4.0 Hz, H-6), 5.85 (1 H, dddd, J = 11.0, 8.5, 3.5, 2.5 Hz, H-7), 5.88 (1 H, ddd, J = 15.5, 5.5, 1.5 Hz, H-4). ¹³C NMR (CDCl₃, 100 MHz) δ 27.14, 29.69, 32.08, 33.78, 38.81, 58.52, 60.41, 64.61, 69.09, 70.92, 73.99, 75.39, 77.15, 83.36, 87.47, 125.69, 128.55, 133.76, 135.17, 177.28, 178.04. ESI Q-TOF MS calcd for C₂₇H₄₄NaO₉ [M + Na]⁺ 535.288, found 535.289. [α]_D ²⁷ +60.7 (c 0.11, CHCl₃).