Objectives: Health inequities are frequently driven by social determinants of health (SDOH) and structural determinants of health. Our pilot sought to test the feasibility of screening for health literacy (HL) and perceived health care discrimination (PHD) through a live telephonic-facilitated survey experience with managed care patients.
Study Design: Cross-sectional study.
Available in either enantiomerically pure form through quantitative Grignard procedures from air-stable crystalline complexes (1, 3), the B-γ-TMS propargylic derivatives of the 10-TMS- (2) and 10-phenyl-9-borabicyclo[3.3.2]decanes (4) provide highly selective entries to 2°-allenyl carbinamines (8, 60-85%, 78-99% ee) and their 3° counterparts (13, 62-82%, 95-99% ee) through their additions to aldimines and ketimines, respectively.
View Article and Find Full Text PDFAsymmetric hydroboration of 1,3-cyclohexadiene with 4R produces the allylborane 5RR as essentially a single diastereomer (i.e., no observable 5RS), and its addition to representative aldehydes provides 9RS (52-75%) with excellent selectivity (94-99% ee).
View Article and Find Full Text PDFThe first asymmetric γ-alkoxyallylboration of representative ketones provides β-alkoxy tert-homoallylic alcohols 10 whose diastereoselectivities range from 99% syn (acetophenone) to 99% anti (pinacolone) both with high ee (>95%). This distribution is attributable to the c/t isomerization of the BBD reagents and the greater reactivity of 7 vs 1 and of aromatic vs alkyl ketones. A ketone-based direct synthesis of a fostriecin intermediate and the tert-amine 26 are reported, each with high selectivities.
View Article and Find Full Text PDFThe asymmetric allylboration of N-H aldimines with optically pure trans-4-substituted-2-boryl-1,3-dienes 6 is described. These organoboranes 6 serve as near-perfect asymmetric allylborating agents for N-H aldimines for the preparation of anti-1,2-disubstituted-3,4-pentadien-1-amines 11 as essentially single diastereomers in enantiomerically pure form (>98% de, ≥98% ee). Enantiomerically pure cis-2,3-disubstitued piperidines 12 and α,β-disubstituted-β-amino acids 17 are readily prepared through the standard protocols.
View Article and Find Full Text PDFThe efficient stepwise construction of optically pure trans-4-substituted 2-boryl-1,3-butadienes 6 is described. Hydroboration of 1-alkynes with either enantiomeric form of 3 leads to the pure trans-1-alkenylboranes 4 which undergo addition of alpha-ethoxyvinyllithium followed by a BF(3)-mediated 1,2-B-->C vinylic group migration to provide 6. These organoboranes 6 serve as a new type of asymmetric allylborating agent providing an extremely selective protocol for the preparation of anti-1,2-disubstituted 3,4-pentadien-1-ols 8 as essentially single diastereomers in enantiomerically pure form.
View Article and Find Full Text PDFThe asymmetric gamma-methoxyallylboration of aldehydes with the configurationally very stable 1 gives nonracemic threo-beta-methoxyhomoallylic alcohols 7 (65-93%) with excellent selectivity (96-99% de, 98-99% ee). The corresponding homoallylic amines 10 are obtained from N-H aldimines with similar efficiency (72-96%) and with excellent diastereoselectivity (98% de) but with lower enantioselectivity (56-86% ee). These new reagents provide ready access to a Taxol side chain derivative.
View Article and Find Full Text PDFObjective: The objective of this study was to find risk factors in pregnancy for post-traumatic stress and depression 1 month after childbirth. Furthermore, the relation between post-traumatic stress and depression was explored.
Design: A prospective longitudinal study.
The allylboration of enantiomerically pure N-triisopropylsilyl-alpha-amino aldehydes (2) with B-allyl-10-trimethylsilyl-9-borabicyclo[3.3.2]decanes (1) proceeds cleanly at -78 degrees C, exhibiting essentially complete reagent control.
View Article and Find Full Text PDFThe synthesis of mixed borabicyclodecane (BBD)-derived 1,3-diborylpropenes (trans-1) is described. These new bimetallic reagents are effective for the selective asymmetric allylboration first of ketones (or ketimines) and second of aldehydes (or aldimines). Formed as a thermodynamic mixture of trans regioisomers from cis-1 through a series of 1,3-borotropic shifts, only trans-1 undergoes the monoallylation of ketones.
View Article and Find Full Text PDFThe syntheses of the optically pure asymmetric hydroborating agents 1 (a, R = Ph; b, R = TMS) in both enantiomeric forms are reported. These reagents are effective for the hydroboration of cis-, trans- and trisubstituted alkenes. More significantly, they exhibit unprecedented levels of selectivity in the asymmetric hydroboration of 1,1-disubstituted alkenes (28-92% ee), a previously unanswered challenge in the nearly 50 year history of this reagent-controlled process.
View Article and Find Full Text PDFThe disilylation of alpha-amino acids 1 to provide 2 (72-87%) was achieved without racemization. An unprecedented borane-mediated semi-reduction strategy was devised to convert 2 to stable, isolable oxazaborolidines 3 (100%) which were hydrolyzed to provide 5 (49-60%) as pure, stable compounds. Analysis of the Mosher amides (8) of the gamma-amino esters 7 reveals that < or =2% racemization occurs in the 1 --> 8 conversions.
View Article and Find Full Text PDFSimple Grignard procedures provide methallylboranes 1a and 1b in enantiomerically pure form from air-stable precursors in 98% and 95% yields, respectively. These reagents add smoothly to aldehydes and methyl ketones, respectively, providing branched 2 degrees- (6, 69-89%, 94-99% ee) and 3 degrees- (10, 71-87%, 74-96% ee) homoallylic alcohols.
View Article and Find Full Text PDFThe asymmetric synthesis of alpha-trimethylsilylpropargylic carbamines (7) through the addition of allenylboranes 4 to N-H aldimines is reported. The insertion of TMSCHN2 into enantiomerically pure B-alkynyl-10-TMS-9-borabicyclo[3.3.
View Article and Find Full Text PDFSimple and efficient Grignard procedures are reported for the syntheses of B-allenyl-10-(phenyl)-9-borabicyclo[3.3.2]decane (1) and its B-(gamma-trimethylsilylpropargyl) counterpart (2) in both enantiomeric forms.
View Article and Find Full Text PDF[Structure: see text] The asymmetric synthesis of N-propargylamides through Michael addition of the alkynylborane 1 to N-acylimines is reported. The N-acetylimines provide the best substrates for the process exhibiting high selectivity (56-95% ee) with predictable stereochemistry. In several cases, 5 crystallizes in essentially pure form (97-99% ee) and a single-crystal X-ray structure was also obtained for 5g (R1=R2=Me, R3=o-Cl-C6C4).
View Article and Find Full Text PDFThe simple and efficient asymmetric synthesis of 3 degrees -carbamines 7 from N-TMS enamines (3) and either enantiomeric form of beta-allyl-10-(phenyl)-9-borabicyclo[3.3.2]decane (1) is reported.
View Article and Find Full Text PDFJ Psychosom Obstet Gynaecol
June 2006
Post-traumatic stress was assessed in early and late pregnancy, and 1, 4, 7, and 11 months postpartum by means of questionnaires among 1224 women. Thirty-seven women (3%) had post-traumatic stress (meeting criteria B, C, and D for PTSD) at least once within 1-11 months postpartum. In pregnancy, depression, severe fear of childbirth, 'pre'-traumatic stress, previous counseling related to pregnancy/childbirth, and self-reported previous psychological problems were associated with an increased risk of having post-traumatic stress within 1-11 months postpartum.
View Article and Find Full Text PDF[reaction: see text] The asymmetric propargylboration of aldehydes at -78 degrees C in <3 h with 1 provides silylated alpha-allenyl carbinols 6 (60-87%) in high ee (94% to >98% ee). The reagents 1 are easily prepared in both enantiomeric forms with a simple Grignard procedure and air-stable borinate complexes 2. The ozonolysis of 6 proceeds smoothly through an acylsilane intermediate to give a TMS ester, which is hydrolyzed to the alpha-hydroxy acid quantitatively with water.
View Article and Find Full Text PDFThe simple and efficient syntheses of B-allyl-10-(phenyl)-9-borabicyclo[3.3.2]decane (1) in both enantiomeric forms are reported.
View Article and Find Full Text PDFIn this study, the authors evaluated the feasibility and efficacy of a binge drinking prevention intervention for college students delivered via the Internet versus a parallel print-based intervention delivered via postal mail. A total of 116 college students completed the baseline survey. The authors then randomized the students into the Web or print group and sent them intervention materials.
View Article and Find Full Text PDFThe remarkable versatility and selectivity of the 10-(trimethylsilyl)-9-borabicyclo[3.3.2]decanes (10-TMS-9-BBDs) in the allyl- and crotylboration of representative aldehydes are reported.
View Article and Find Full Text PDFThe asymmetric allenylboration of representative aldehydes with the stable, storable 1 is reported. Easily and efficiently prepared in either enantiomeric form from the air-stable crystalline 4 through simple Grignard procedures, 1 gives 6 cleanly. The latter is easily isolated in high yield and ee with predictable stereochemistry.
View Article and Find Full Text PDF