On the halogenation of N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid esters and the conformational preferences of their 5-halo-piperazic acid products. The importance of A1,3 rotameric-strain in determining N(2)-acyl piperazic acid ring conformation

In this Letter, an unambiguous synthetic strategy is reported for the preparation of enantiomerically purecis-5-halo-piperazic acid derivatives in single diastereoisomer form. Contrary to the recent report by Shin and co-workers (Chem. Lett. 2001, 1172), in which it is claimed that the Ph₃P and N-chlorosuccinimide (NCS)-mediated chlorination of (3R,5S)-trans-N(1),N(2)-di-t-Boc-5-hydroxy-piperazic acid derivative 1proceeds with retention of configuration at C(5) to give 2, we now show that this and related Ph₃P-mediated halogenations all occur with S_N2 inversion at the alcohol center, as is customary for such reactions. Specifically, we demonstrate that the (3R,5S)-trans-5-Cl-piperazic acid derivative 2 claimed by Shin and co-workers (Chem. Lett. 2001, 1172) is in actual fact the chlorinated (3S,5R)-enantiomer 6, which must have been prepared from the cis-(3S,5S)-alcohol 3, a molecule whose synthesis is not formally described in the Shin paper. We further show here that the cis-(3R,5R)-5-Cl-Piz 13 claimed by Shin and co-workers inChem. Lett. 2001, 1172, is also (3S,5R)-trans-5-Cl-Piz 6. Authentic 13 has now been synthesized by us, for the very first time, here. Since Lindsley and Kennedy have recently utilized the now invalid Shin and co-workers’ retentive Ph₃P/NCS chlorination procedure on 1 in their synthetic approach to piperazimycin A (Tetrahedron Lett. 2010, 51, 2493), it follows that their claimed 5-Cl-Piz-containing dipeptide 25 probably has the alternate structure 26, where the 5-Cl-Piz residue has a 3,5-cis-configuration. The aforementioned stereochemical misassignments appear to have come from a mix-up of starting materials by Shin and co-workers (Chem. Lett. 2001, 1172), and an under-appreciation of the various steric and conformational effects that operate in N(2)-acylated piperazic acid systems, most especially rotameric A^1,3-strain. The latter has now been unambiguously delineated and defined here under the banner of the A^1,3-rotamer effect.

Spacing Commemorative-related Violence in Northern Ireland: Assessing the implications for a society in transition

This paper explores the geography of commemorative-related violence in Northern Ireland and considers its ramifications for a society in transition. Using original primary research, this article contributes to discussions on violence, space and memory through a spatial analysis of new quantitative archival data and existing archival material explored through a multi-disciplinary lens. It examines the complex relationship between the practices and processes of commemoration, the violence that it sometimes occasions and the places in which such violence exists. In unpacking this specific form of violence we consider the continued importance of both place and past in a post-conflict society. This includes a concern for the changing structures and forms of governance that influence how the past is negotiated as Northern Ireland marks a decade of commemorations leading up to the centenary of its contested creation.

Letter, Chatham, to Colonel Calvin Spencer, Chesterfield, SC, 1790 July 3

This letter is from J. A. Dibble to Calvin Spencer regarding William Lides with enclosed papers; these papers were not present with the letter when scanned.

Letter, Elmwood, SC, from Annie Causey Walsh, Chesterfield, SC, 1869 April 27

This letter is from Annie, niece of Sarah Spencer, to her cousin. She writes of the well being of her family, her relations, and how she is currently living.

Letter, Petersburg, VA, to Colonel Calvin Spencer, Chesterfield, SC, 1787 September 26

This letter is from Jerman (?) Baker to Colonel Calvin Spencer.

Letter, Greensboro, NC, to George Washington Spencer, Chesterfield, SC, 1890 January 11

This letter is from G. W. Winstead and A. M. Scales to G. W. Spencer regarding Reverend Dr. J. W. Blosser.

Letter, to Colonel Calvin Spencer, Chesterfield, SC, 1780 February 18

This letter is from Alex Outlaw to Colonel Calvin Spencer.

Letter, to Colonel Calvin Spencer, Chesterfield, SC, c. 1700 October

This letter is from E. Waterman to Colonel Calvin Spencer.