Протекание аллиназных реакций

Исследования показали, что для протекания аллиназных реакций необходимо участие еще одного соединения — кофактора, называемого пи- ридоксальфосфатом. Участие кофактора в реакции, вероятно, состоит в том, что он взаимодействует с субстратом, переводя его в активированную форму. Оснбвная (т.е. захватывающая протон) группа фермента инициирует образование сульфеновой кислоты. Сульфеновые кислоты по природе своей крайне неустойчивы, и спонтанно превращаются в другие продукты.

Я занялся химией чеснока и лука в 1971 г., начав с более глубокого исследования свойств аллицина. Вместе с коллегами из Миссурийского университета в Сент-Луисе мы изучали химические превращения метил- метантиосульфината CH3S(0)SCH3. Это соединение — простейший гомолог аллицина: в нем также есть группа S(0)H, определяющая химические свойства аллицина, но углеродный

скелет молекулы имеет более простое строение. Дж. О’Коннор и я обнаружили два необычных химических процесса (см. нижний рисунок на с. 62). В первом из них происходит распад ме- тилметантиосульфината с образованием метансульфеновой кислоты СН3— SOH и тиоформальдегида CH2 = S. Метансульфеновая кислота — очень реакционноспособное соединение; ее молекулы взаимодействуют друг с другом попарно (при этом освобождается по одной молекуле воды), так что вновь образуется метилметантиосульфинат. Второй процесс — это конденсация молекул метилметантиосульфината; продуктом реакции является 2,3,5-тритиа- гексан-5-оксид CH3S(0)CH2SSCH3.

Через двенадцать лет эта работа очень пригодилась в исследованиях механизма образования антитром- бозного фактора чеснока. М. Джейн и Р. Крисли из Делавэрского университета вместе с Р. Акиц-Кастро и М. Крус из Венесуэльского института научных исследований в Каракасе получили несколько различных экстрактов чеснока, которые очень эффективно препятствовали агрегации тромбоцитов крови. Наиболее активный экстракт содержал соединение с химической формулой C9H14S30. В тесном сотрудничестве с коллегами из Делавэрского университета и Венесуэльского института С. Ахмад и я, работая в Университете шт. Нью-Йорк в Олбани, установили структуру этого соединения: CH2 = CHCH2S(0)CH2CH = = CHSSCH2CH = СН2 или 4,5,9-три- тиадодека-1,6,11 -триен-9-оксид. Мы назвали его ajoene (айоен *) от испанского ajo (произносится «ахо»), что означает «чеснок».

 

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