Asymmetric synthesis with the robust and versatile 10-substituted 9-borabicyclo[3.3.2]decanes: Homoallylic amines from aldimines

Hernandez, Eliud; Canales, Eda; Gonzalez, Eduvigis; Soderquist, John A.

doi:10.1351/pac200678071389

Pure Appl. Chem., 2006, Vol. 78, No. 7, pp. 1389-1395

http://dx.doi.org/10.1351/pac200678071389

Asymmetric synthesis with the robust and versatile 10-substituted 9-borabicyclo[3.3.2]decanes: Homoallylic amines from aldimines

Eliud Hernandez, Eda Canales, Eduvigis Gonzalez and John A. Soderquist

University of Puerto Rico, Department of Chemistry, Rio Piedras, 00931-3346, Puerto Rico

Abstract: The asymmetric allylboration of N-H aldimines, generated from either N-trimethylsilyl or N-diisobutylalanyl precursors, with B-allyl-9-borabicyclo[3.3.2]decane is described. The desired homoallylic amines are obtained efficiently (60-90 %) and selectively (60-89 % ee). A non-oxidative work-up procedure has also been developed for this new method, which permits the recovery of the air-stable pseudoephedrine (PE) complex (50-70 %), which is conveniently converted back to B-allyl-9-borabicyclo[3.3.2]decane (98 %) with allylmagnesium bromide in ether for its reuse in the asymmetric allylboration process. Additional studies were conducted to better understand these processes and the origin of the observed enantioselectivity.