Re: fused benzene strut (jmichels@ea.oac.uci.edu)
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18 Apr 1996 13:17:46 -0400

        CH                            CH      +
      CH  C-CH2Br + :PPh3 ------->  CH  C-CH2-PPh3 + 2Br-    (phosphonium 
      CH  C-CH2Br + :PPh3           CH  C-CH2-PPh3               salt)
        CH                            CH      + 
 

Deprotonation with n-butyl lithium (or probably a milder base) to give double ylid

        CH      +                         CH  -  + 
      CH  C-CH2-PPh3 + 2LiC4H9- ------> CH  C-CH-PPh3 + 2LiBr + 2C4H10
      CH  C-CH2-PPh3                    CH  C-CH-PPh3
        CH      +                         CH  -  +
 
 Addition to 2,3-butanedione
                                       
   CH  -  +          CH3             CH CH
 CH  C-CH-PPh3  +  O=C    ------>  CH  C  C-CH3
 CH  C-CH-PPh3     O=C             CH  C  C-CH3
   CH  -  +          CH3             CH CH
 

4 step, 4 carbon addition

------>                         CH CH CH

--------> CH C C C-CH3
--------> CH C C C-CH3 repeat... ----------> CH CH CH

This structure might be useful unfunctionalized, but, since it's symmetrical, would be hard to attach groups on one side only. Of course, you could put groups on both sides simultaneously, but would be wasteful if they were motor binding sites.

Convergently would go faster:

   CH CH                                     CH CH
 CH  C  C-CH3 + NBS, 2PPh3, 2RLi,         O=C  C  C-CH3
 CH  C  C-CH3                             O=C  C  C-CH3
   CH CH                                     CH CH
         
------>                        

-------->
--------> ----------> CH CH CH CH CH CH C C C C C-CH3 CH C C C C C-CH3 CH CH CH CH CH

4 step, 12 carbon addition.

I'm currently trying to find the stiffest, easiest to synthesize, easiest to functionalize on one side (or leave it bare) potential strut.

John Michelsen