Kerr K M, Kook A M, Davis P J
J Nat Prod. 1986 Jul-Aug;49(4):576-82. doi: 10.1021/np50046a003.
The aporphine alkaloid glaucine (1) was examined by comparison of the high field (600 MHz) 1H-nmr spectra of 1 vs. racemic 6a,7,7-trideutereoglaucine (4,5), by computer-simulated 1H-nmr spectra at 600 MHz, by using decoupled proton spectra, and two-dimensional COSY and HETCOR experiments with 1 at 500 and 360 MHz, respectively, and using high field (90 MHZ) 13C-nmr of S-(+)-glaucine (1). Emphasis was placed on the resolution of the chemical shifts and coupling constants for the H-4 alpha, H-4 beta, H-5 alpha, H-5 beta, H-6 alpha, H-7 alpha, and H-7 beta alicyclic protons of the molecule, which were previously unassigned. The complete assignment of the alicyclic protons of 1 by 1H-nmr was required for the structural elucidation of deuterated analogs of glaucine, which will be used in microbial transformation studies to determine the stereochemical course of aporphine dehydrogenation by the fungi Fusarium solani (ATCC 12823) and Aspergillus flavipes (ATCC 1030).
通过比较青藤碱（1）与外消旋6a,7,7-三氘代青藤碱（4,5）在高场（600 MHz）的1H-核磁共振谱、利用计算机模拟600 MHz的1H-核磁共振谱、使用去耦质子谱以及分别在500 MHz和360 MHz对1进行二维COSY和HETCOR实验，并利用S-(+)-青藤碱（1）的高场（90 MHz）13C-核磁共振谱，对阿朴啡碱生物碱青藤碱（1）进行了研究。重点在于解析该分子中H-4α、H-4β、H-5α、H-5β、H-6α、H-7α和H-7β脂环族质子的化学位移和耦合常数，这些质子之前未被归属。通过1H-核磁共振对1的脂环族质子进行完全归属，对于青藤碱氘代类似物的结构解析是必要的，这些类似物将用于微生物转化研究，以确定茄病镰刀菌（ATCC 12823）和黄曲霉（ATCC 1030）对阿朴啡碱脱氢的立体化学过程。
