New Route for the Synthesis of (22S,23S)-28-Homobrassinolide

Abstract

A new and highly efficient synthesis of (22S,23S)-28-homobrassinolide (3) has been achieved. (2α,3α,22S,23S)-Tetrahydroxy-5α-stigmastan-6-one (4), a key intermediate for the synthesis of 3, and (2α,3α)-dihydroxy-5α-stigmast-22-en-6-one (6), a versatile intermediate for the synthesis of 3, and several naturally occurring brassinosteroids have been obtained in excellent yield from stigmasta-2,(22E)-dien-6-one (5) by catalytic RuO₄ hydroxylation. Sodium perborate, a cheap and large-scale industrial chemical is used for Baeyer-Villiger oxidation of B-ring ketone 9 to its lactone 10.

brassinosteroids - dihydroxylation - plant growth promoters - ruthenium tetroxide - sodium perborate

References

<A NAME="RT10002SS-1">1</A> Grove MD. Spencer WK. Rohwedder WK. Mandava N. Worley JF. Warthen JD. Steffens GL. Flippen-Anderson JL. Cook JC. Nature (London)  1979,  281:  216 

<A NAME="RT10002SS-2A">2a</A> Adam G. Marquardt V. Phytochemistry  1986,  25:  1787 

<A NAME="RT10002SS-2B">2b</A> Lakhvich FA. Khripach VA. Zhabinskii VN. Russ. Chem. Rev.  1991,  60:  658 

<A NAME="RT10002SS-2C">2c</A> Cutler HG. Yokota T. Adam G. Brassinosteroids-Chemistry, Bioactivity and Applications, ACS Symposium Series No. 474   American Chemical Society; Washington D.C.: 1991. 

<A NAME="RT10002SS-2D">2d</A> Marquardt V. Adam G. In Chemistry of Plant Protection   Vol. 7:  Ebing W. Springer; Berlin: 1991.  p.103 

<A NAME="RT10002SS-2E">2e</A> Sakurai A. Fujioka S. Plant Growth Regulator  1993,  13:  147 

<A NAME="RT10002SS-2F">2f</A> Cutler HG. Advances in the Use of Brassinosteroids, ACS Symposium Series No. 551   American Chemical Society; Washington D.C.: 1994.  p.85 

<A NAME="RT10002SS-2G">2g</A> Back TG. In Studies in Natural Product Chemistry  Vol. 16; Atta-Ur-Rahman, Ed.; Elsevier; Amsterdam: 1995.  p.321 

<A NAME="RT10002SS-2H">2h</A> Adam G. Porzel A. Schmidt J. Schneider B. Voigt B. New Developments in Brassinosteroid Research, In Studies in Natural Products Chemistry  Vol. 18; Rahman, Ed.; Elsevier; Amsterdam: 1996.  p.495-549  

<A NAME="RT10002SS-2I">2i</A> Hazra BG. Pore VS. J. Indian Chem. Soc.  1998,  75:  746 

<A NAME="RT10002SS-2J">2j</A> Brosa C. Biological Effects of Brassinosteroids, Critical Review in Biochemistry and Molecular Biology  1999,  34:  339 

<A NAME="RT10002SS-3A">3a</A> Li J. Nagpal P. Vitart V. McMorris TC. Chory J. Science  1996,  272:  398 

<A NAME="RT10002SS-3B">3b</A> Szekeres M. Nemeth K. Koncz-Kalman Z. Mathur J. Kauschmann A. Altmann T. Redei GP. Nagy F. Schell J. Koncz C. Cell  1996,  85:  171 

<A NAME="RT10002SS-4">4</A> Thompson MJ. Meudt WJ. Mandava NB. Dutky SR. Lusby WR. Spaulding DW. Steroids  1982,  39:  89 

<A NAME="RT10002SS-5">5</A> Wada K. Marumo S. Agric. Biol. Chem.  1981,  45:  2579 

<A NAME="RT10002SS-6">6</A> Takatsuto S. Ikekawa N. J. Chem. Soc., Perkin Trans. 1  1984,  439 

<A NAME="RT10002SS-7">7</A> Mori K. Sakakibara M. Ichikawa Y. Ueda H. Okada K. Umemura T. Yabuta G. Kuwahara S. Kondo M. Tetrahedron  1982,  38:  2099 

<A NAME="RT10002SS-8">8</A> Hazra BG. PavanKumar T. Joshi PL. Liebigs Ann. Chem.  1997,  1029 

<A NAME="RT10002SS-9">9</A> Kamuro Y. Takatsuto S. Brassinosteroid Conference, 27-31 August   American Chemical Society; Washington D.C.: 1990. 

<A NAME="RT10002SS-10">10</A> Rodrick JG. Guan M. Brassinosteroids and Root Development in Brassinosteroids: Chemistry, Bioactivity and Applications, ACS Symposium Ser. 474   Cutler HG. Yokota T. Adam G. American Chemical Society; Washington D.C.: 1991.  Chap. 20.

<A NAME="RT10002SS-11">11</A> Schilling G. Schiller C. Steffan O. Influence of Brassinosteroids on Organ Relations and Enzyme Activities of Sugar-Beet Plants in Brassinosteroids: Chemistry, Bioactivity, and Applications, ACS Symposium Ser. 474   Cutler HG. Yokota T. Adam G. American Chemical Society; Washington D.C.: 1991.  Chap. 18.

<A NAME="RT10002SS-12">12</A>

Godrej Agrovet Ltd. Mumbai, India, has commercialised (22S,23S)-homobrassinolide for the enhancement of yields of paddy, wheat, tomato, cabbage, cauliflower, potato, groundnut (peanut), cotton, grapes and tea.

<A NAME="RT10002SS-13A">13a</A> Hazra BG. Pore VS. Joshi PL. J. Chem. Soc., Perkin Trans. 1  1993,  1819 

<A NAME="RT10002SS-13B">13b</A> Hazra BG. Joshi PL. Bahule BB. Argade NP. Pore VS. Chordia MD. Tetrahedron  1994,  50:  2523 

<A NAME="RT10002SS-13C">13c</A> Hazra BG. Basu S. Bahule BB. Pore VS. Vyas BN. Ramraj VM. Tetrahedron  1997,  53:  4904 

<A NAME="RT10002SS-14">14</A> For the oxidation of organic compounds by ruthenium tetroxide, see: Lee DG. Van den Engh M. In Oxidation in Organic Chemistry   Part B:  Trahanovsky WS. Academic Press; New York: 1973. 

<A NAME="RT10002SS-15">15</A> Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 

<A NAME="RT10002SS-16A">16a</A> Shing TKM. Tai VW.-F. Tam EKW. Angew. Chem., Int. Ed. Engl.  1994,  33:  2312 

<A NAME="RT10002SS-16B">16b</A> Shing TKM. Tam EKW. Tetrahedron Lett.  1999,  40:  2179 

<A NAME="RT10002SS-17">17</A> Mulvihill MJ. Miller MJ. Tetrahedron  1998,  54:  6605 

<A NAME="RT10002SS-18">18</A> Thompson MJ. Mandava N. Meudt WJ. Lusby WR. Spaulding DW. Steroids  1981,  38:  567 

<A NAME="RT10002SS-19">19</A> Takatsuto S. Ikekawa N. Chem. Pharm. Bull.  1982,  30:  4181 

<A NAME="RT10002SS-20">20</A> Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 

<A NAME="RT10002SS-21">21</A> Mori K. Sakakibara M. Okada K. Tetrahedron  1984,  40:  1767 

<A NAME="RT10002SS-22">22</A> Takatsuto S. Ikekawa N. J. Chem. Soc., Perkin Trans. 1  1983,  2133 

<A NAME="RT10002SS-23">23</A> Sharpless KB. Akashi KJ. J. Am. Chem. Soc.  1976,  98:  1986 

<A NAME="RT10002SS-24">24</A> Okada K. Mori K. Agric. Biol. Chem.  1983,  47:  89 

<A NAME="RT10002SS-25">25</A> McKillop A. Tarbin JA. Tetrahedron  1987,  43:  1753