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Chemical Synthesis

LAB Reagents

Lithium aminoborohydride (LAB) reagents are a new class of powerful and selective reagents developed in the laboratory of Professor Bakthan Singaram at the University of California, Santa Cruz.

These reagents have reactivity comparable to lithium aluminum hydride (LiAH4). However, LABs have several advantages over LiAlH4 in that they are air-stable, nonpyrophoric, thermally stable, and liberate hydrogen only slowly in protic solvents above pH 4. Thus, LABs can reproduce in air virtually all of the transformations for which LiAlH4 is commonly used, and offer an attractive alternative due to advantages in safety, selectivity, ease of handling, and simple work-up procedures. LABs are capable of reducing a variety of functional groups summarized in Scheme 1.1



In the case of N-alkyl lactams with an ester group, LAB can be used to selectively reduce the ester at reduced temperature, leaving the lactam intact. At an elevated temperature, the lactam also reduces to form the cyclic amine (Scheme 2).2



In addition to hydride transfer, LABs can transfer the amine moiety, as in the case of reaction with halopyridines (Scheme 3)3 and primary alkyl methanesulfonates (Scheme 4).4 Alkyl methanesulfonates can be reduced to the corresponding alkanes with LAB reagents if Et3B is added in substoichiometric amounts (Scheme 5).4







The LAB reagents ability to function as both a reducing agent and amination reagent allows the researcher to perform tandem amination-reduction reactions, as in the case of reaction with when 2-halobenzonitriles are used as a substrate.5 The LAB reagent activates the halobenzonitrile toward nucleophilic attack by the amine moiety of the LAB reagent. This protocol is particularly effective with 2-fluorobenzonitrile (Scheme 6).



Product Name Product # 
Lithium dimethylaminoborohydride solution, 1M in THF  658235
Lithium morpholinoborohydride solution, 1M in THF  658308
Lithium pyrrolidinoborohydride solution, 1M in THF  658243

References:

  1. Fisher, G. B. et al. J. Org. Chem. 1994, 59, 6378. For a recent review, see: Pasumansky, L. et al. Aldrichimica Acta 2005, 38, 61.
    (a) Collins, C. J.; Singaram, B. ARKIVOC 2001, 4, 59.
    (b) Flaniken, J. M. et al. Org. Lett. 1999, 1, 799.
  2. Thomas, S. et al. Org. Lett. 2003, 5, 3867.
  3. Thomas, S. et al. Org. Lett. 2001, 3, 3915.
  4. Thomas, S. et al. J. Org. Chem. 2001, 66, 1999.